JPH06504628A - UV/EB curable butyl copolymers for lithography and anti-corrosion coating applications - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] UV/EB curable butylcoat for lithography and anti-corrosion coating applications polymer The present invention relates to lithography (lilhofrsph7), corrosion prevention, and its Isoolefins and para-alkylstyrenes incorporated in other coatings ultraviolet (UV) and electron beam (EB) reactive functionalized copolymers of Regarding. More specifically, the present invention provides radiation curable Such copolymers, coatings, in which alkylstyrenes are functionalized, And regarding the method.

Background of the invention Techniques that use radiation-sensitive functional groups to cause crosslinking of polymeric materials are particularly A developing technology in the photographic industry where photographic film is composed of light-sensitive polymers. It is. However, it is also possible to incorporate EB or UV crosslinkable functional groups into rubber elastic polymers. desirable. Elastomers with such functional groups are radiation curable, adhesive strength and pressure sensitive adhesive to give excellent resistance to temperature, abrasion, solvents and ozone It could be used in agents and coatings.

Methods using external crosslinking agents have some inherent difficulties. Such an arrangement The elastomer can be treated with a photoinitiator or crosslinking agent to facilitate the curing process. It requires that Manufacturing difficulties due to the toxicity and volatility of these compounds and may be dangerous. PSA and coatings are sensitive to external free radicals. Contains highly reactive unsaturated sites in the main chain of the polymer to facilitate crosslinking. Depending on the polymer, unsaturation also means that the backbone is free of radicals. provides a site that can be cleaved for the desired reaction.

U.S. Patent No. 4.556.4, awarded to St. Flair (SLCIsir). In No. 64, block A is polystyrene/isoprene or polystyrene/butadiene. block polymer A, in which block B is polyisoprene; A formulation of BA, a tackifier compatible with block B, and a tackifier compatible with block A. Radiation curable adhesive composition suitable for use as a PSA, comprising a crosslinking agent is disclosed.

Can be cross-linked without the use of these additive compounds and can be dissociated during reactions involving radicals. It is desirable to obtain PSAs and coatings with saturated polymer backbones that do not stomach.

Therefore, alternatively, e.g. Radiation-reactive crosslinkers can be incorporated into the polymer backbone by Ru.

It is generally difficult to produce such comonomers on a large scale. radiation-responsive agent Functional groups can also be grafted onto the polymer backbone in a post-polymerization step, but Because it is difficult to achieve proper molecular contacts at the desired reaction site, The resulting polymers are generally heterogeneous products with low yields. Photochemical reactions in polymers Mechanisms and examples of photoinitiators are incorporated herein by reference, J.F. Rsdek's Mechanisms on Photophysical Processes AND Photochemical Reactions・Jinha Polymersφ Theory〇and・ Applications (Mechxniu+stri Phophoph7sic xlProcesses and Pholockeiicxl Rexcli on+ in Po17mersTheor7 znd Apicalioi +l J, Chapters 1I and 12, J, Wile & Sons (1, Wiler & 5ons), 1987.

European Patent Application No. 17,364 describes the allyl benzoyl benzoate comonomer and a monoethylenically unsaturated polymerizable comonomer from 0.1 to 10 copo prepared by incorporating % by weight and cured by actinic radiation such as UV light. Rimmer is disclosed. These polymers are used in coating and impregnating formulations. and has been described as useful in adhesive, caulk and sealant formulations. There is.

U.S. Patent No. 4.315.99 to Necker+ et al. No. 8 is a polymeric material that incorporates photosensitive functional groups via a nuclear substitution reaction. Disclosed. This polymeric material is the basis for heterogeneous catalysis of various photoinitiated chemical reactions. (platfo 'm).

U.S. Pat. No. 4,188.215 to Safe et al., Fukuta No. 3.923.703 to FukuNni et al. Nos. 3.867 and 318 given to ishikebo and others, thistle (Axx ii) No. 3.694.3113 and Reynolds (Rty+ 3.560.465 and British Patent No. 1.341. No. 004 all contain polymer resins with photosensitive functional groups and/or those resins. Relating to a manufacturing method. These photopolymer resins are generally useful in photographic films. Ru.

A photosensitive coating containing a blend of a polymer and a photosensitive crosslinker is Malatesta (M alxfeslzl et al., U.S. Pat. No. 3,86? , No. 271.

In this patent, conjugated diene-containing butyl rubber is produced with the help of a specific photosensitizer. Harden with external lines. Said to be useful as a coating for glass supports Similar compositions are disclosed by Tobias (T+l+1ttl et al., U.S. Pat. No. 4,086,3). No. 73 contains at least a rubbery thermoplastic organic polymer and an organic photosensitizer. are disclosed.

Photosensitive vinyl monomers are disclosed in Skoaltchi, U.S. Pat. ．． No. 429.852 and No. 3,574,617, but herein , ethylenically unsaturated derivatives of substituted benzophenones, Ethylenically unsaturated reactants such as dily acrylate or glycyl methacrylate produced by a method comprising reacting with. The resulting monomer is then isolated Polymerized or various conventional ethylenically unsaturated monomers, i.e. vinyl monomers It can be copolymerized with. Photosensitive coating systems are made using organic solvents or emulsions. It is manufactured by depositing a solid polymer from a polymer onto a support. This photosensitive The chemical coating can be applied, for example, by lithography and etching (chemical It is described as being particularly suitable for use in a variety of applications involving lliBl.

A similar concept is described in Wing7 U.S. Pat. No. 4,1411.9117. However, herein, substituted benzophenone or acetophenone monoesters are disclosed. Thyrenic unsaturated derivative, benzophenone or acetophenone to vinylbenzyl It is produced by reacting with halide. Polymerize these derivatives to make homogeneous polymers or copolymers with a wide range of conventional ethylenically unsaturated monomers. Ru. The resulting polymer has wavelengths between 2.000 and 5.000 angstroms. Sensitive to radiation such as ultraviolet light and exposed to such radiation It crosslinks or hardens easily when exposed to water. Adhesive, binder, coating, and impregnating compositions Products are manufactured from these polymers.

Radiation-sensitive functional groups are used in the printing industry to induce crosslinking of polymeric materials. The printing plate is first coated with a photosensitive polymer. will be processed. Such radiation-crosslinkable polymers are suitable for semiconductor or other engraved articles. It has also been widely used in manufacturing as a photoresist.

A method for functionalizing polymers with radiation-curable moieties was developed by Jones (1ones). It is disclosed in National Patent No. 4.112.201, but here, a pendant-shaped Butadiene or isoprene copolymers with unsaturated tetraaliphatic quaternary nitrogen moieties (e.g. those derived from acrylic esters and acrylamide) are water-soluble or as an inherently dispersive curable coating. coat like this Coatings include protective and/or decorative coatings, coatings on paper, textile fibers. Photocurable imaging for coatings, printing plates, photoresists and lithography plates It is useful as a component material, etc. These coatings are light, high energy An insoluble cross-linked coating that can be cured thermally in the presence of radiation and radical catalysts. It is described that it forms a ring. These polymers undergo amination and post-polymerization reactions. Manufactured by Similarly, p-hydro of poly(vinylbenzyl chloride) xybenzophenone, p-hydroxyfluorenone, carbazole potassium, and Modification with photosensitive compounds, including and the like, has been described by Bayley (BsilrJ et al. Nal on Applied Polymer Science; Polymer Chemistry Edijon (Jow+ntl of Applied Po17me+5c ie++ce:　Po17+aerChsmitjty　Ed,), Volume 17, 777-182 (1980).

Journal on Apply by Azuma (811111) and others is cis-1,4- A pendant compound containing polybutadiene and cinnamoyl groups The properties and method of preparation of polybentenamers having n+) functional groups are disclosed. S The introduction of a annamoyl group into a bentanamer has, for example, a hydroxymethyl group. By reacting polypentenamer with cinnamoyl chloride. Cinnamomolization Relationships involving the photosensitivity of polypentenamers are described.

For example, the cis reaction of an α,β-unsaturated carboxylic acid such as cinnamic acid in the presence of an acid catalyst. -1,4-polybutadiene, 1,2-polybutadiene and po-jbentheamer Addition reactions to fuboridienes are disclosed. to unsaturated polydiene cyclization occurs in competition with the incorporation of the carboxylic ester group. Polymer morphology The logic consists of blocks alternating between cyclic segments and embedded segments. It is stated that it shows a block-shaped segment. This polymer consists of two glass It is noted that the degree of incorporation and cyclization can be controlled by reaction conditions. Cis-1,4-polybutadiene with pendant cinnamate groups is listed. of photosensitive cyclized polydienes, such as polymers and polypentenamers, Discloses research on relationships. Photodimerization of the cinnamate group results in an increase in the mobility of the group. It has been stated that the greater the degree of cyclization, the more the photosensitivity decreases. Ru.

et al., polyisoprene was reacted with maleic anhydride in 0-dichlorobenzene solution. to produce α-substituted anhydride hook acid group-modified polyisoprene, and further, To incorporate cinnamate groups, this polyisoprene was oxidized in pyridine. It is known to be modified by reacting with ethyl cinnamate. 75 moles of repeating group It was noted that up to 1% of the samples were easily incorporated. Modified polyisoprene feel The optical properties of cinnamate-modified polyesters are due to the interaction of free carboxylate groups. It is said to be larger than Pentenamer. This interaction causes the polymer segment (S The dependence of photosensitivity on the mobility of Bme++t) was reduced.

The production and use of copolymers of styrene and isobutylene are known in the art. be. Therefore, tough, glassy polystyrene content for plastic blends From copolymers with high styrene content to rubbery materials used in impact modifiers, Such copolymers ranging up to low copolymers are well known in the art. ing.

In the past, styrene and isobutylene were rather easily synthesized under cationic polymerization conditions. were copolymerized to yield these copolymers over the entire composition range. Also, Bawa No. 3.948.1168 to Pave rυ By changing the copolymerization conditions, block-like or random It is also known that homogeneous copolymers can be produced using This patent is in fact Lander containing two or more types of cationically polymerizable monomers such as tyrene and styrene describes the production of uniform polymers. This disclosure also covers various olefinization contains a long list of compounds, including isobutylene, styrene, Contains tyrene and other olefin compounds. Additionally, these compounds takes advantage of the surface properties of polyisobutylene arrays and combines them with other materials to create adhesives. as a coating, asphalt blend, and various plastics. It is widely used, including in last tip rends.

Terpolymers containing isoprene as described in the '868 patent It is also well known to produce terpolymers, but the overall The molecular weight of poly÷- decreases. Therefore, the production of high molecular weight polymers from them becomes difficult and the whole production process becomes complicated.

Attempts have also been made to produce various functionalized polymers. For example, U.S. Patent No. 3, issued to Hinke et al. ．． No. 145.187 is salt polyvinyl chloride polymers, surfactants and chlorinated olefin polymers. Discloses Marblend. And this olefin polymer has numerous other Among the compounds of These include copolymers of various materials that can be It is stated that the mer can be chlorinated by known methods.

The literature also reveals other methods for producing copolymers of isobutylene and styrene. A method is disclosed. For example, copolymerization of isobutylene with halomethylstyrene Bowers, U.S. Pat. No. 4,074.034, issued to It is as shown below. This method uses vinylbenzyl chloride as the starting material. and the monomers are soluble under defined conditions. Certain continuous solution processes using certain solvents or mixed solvent systems are used. expensive vinyl Apart from the need to use nylbenzyl chloride starting material, these methods have Additionally, this method can be used without excessive chain branching and gel formation during polymerization. In terms of the amount of aromatic chloromethyl functional group that can be incorporated, and the cationic weight No. 16, pp. 452-459 due to the reactivity of benzylchlorine under (1969), “Isobutylene Copolymers on Vinylbenzyl Chloride” "Isopropenylbenzyl chloride" ("l5obutylen") eCopol Years of Yin71benBI Chloride 1 1111110111O-pen71beu71 Chloride”) I want to be illuminated. Among these, aromatic monomers are a mixture of para and meta isomers. Are listed.

There is also interest in halomethylation of isobutylene/styrene copolymers. example For example, the paper by Sajikotsu et al., ``Chloromethylation ・On-an isobutylene styrene copolymer and some on iso ・Chemical Actions” (“Chloro-mNbyls eyes oa of l+ob++t71eneslyrcoe C+pol)mer　1n+.

Article by Harris (glatis et al.), “Block and Graft Co. Polymers on Bivalolactone, J (”Block xn In d Gttlj Copo17mers ol, the authors found that isobutylene copolymerization with styrene and, preferably, ring methylated styrene.

This article specifically describes a mixture of meta- and para-methylstyrene in a quantitative ratio of about 65/35. Discloses copolymerization with vinyltoluene and with paramethylstyrene containing , whose purpose is to create an autooxidizing, aliphatic unsaturation-free, thermoplastic rubber-elastic PIVA Production of rolactone copolymer system. This article is about vinyl toluene and Not aware of the difference in the use of tylstyrene. And in any case, In unfractionated copolymers, even when using para-methylstyrene, It has copolymers with properties such as non-uniform compositional distribution and very broad molecular weight distribution. conditions are adopted. In other words, as stated in Tables 4 and 5, In the fractionated copolymer, Mn is 16.000 and Mw/Mn is 17.000. 45, and the 4-methylstyrene content in the polymer was at the time of monomer supply. and varies significantly as a function of molecular weight.

Finally, copolymers of isobutylene and para-methylstyrene are discussed; Some articles do not discuss how to make them. Those articles include sajikotsu, ho [Studies on Oxidative Thermal Degradation] Copolymers on isobutylene with m-and p-methylstyrene Len-Yin Ken Aφ Solution Op ψ Mineral φ Oils,” (“5tud ie+ol 0td1fite Theretl Dggrsdsjion ofCopo17mers ol Itobaf71e*e vth b m-go d p -Metb71-stytenes in t 5 solution o fMincrsl 0ils, “”) Uch, Zap, Azerb, Un, t, Ser.

K h u m, 1975 (3041, 87-92, and other such Contains articles. In addition, Toman (TOIll■), Haka,'s "Isobutylene" C Polymer Zooando Copolymers with Chondral Structure "(l5obi171ene Polymers sad Copoly iers withCoNrollcd 5ltocture’), A p p, 7g/7, 339, (November 10, 1978), iso There is reference to the copolymerization of butylene with vinyl aromatic monomers. In this way, iso For copolymers of butylene and alkylstyrene of useful molecular weights, and This type of functionalized copolymer can or cannot be crosslinked. Research continues into things that can be used for a wide range of purposes even without them.

Polymers with a saturated hydrocarbon backbone have good environmental and aging resistance This is well known and therefore highly desirable for a wide range of applications. Furthermore, the main quantity A rubbery copolymer containing polyisobutylene with low permeability and unique buffer properties. properties and low surface energy, making it especially highly desirable in many applications. It is also well known that However, these saturated hydrocarbon polymers 'inertness', low reactivity and incompatibility with many other substances, and that they are difficult to glue or use in combination with many other materials Due to these reasons, their use is restricted in many fields.

Co-assigned U.S. Application No. 441,575, filed Nov. 22, 1989. No. 416,5, filed Oct. 3, 1989, also co-pending. This is a partial continuation of No. 03, and Nos. 416 and 503 are both pending applications, May 1988 Filed on May 27, U.S. Application No. 199.665 and its continuation in part, both pending. filed on May 3, 1989, continuation in part of U.S. Application No. 416.713. These disclosures have been cited in this book, but the following is theorized: It was. That is, controlled amounts of specific desired functional groups can be saturated as pendant groups. When introduced onto a Japanese hydrocarbon backbone, these polymers adhere to other surfaces and/or or react with other functional polymers by "grafting" or crosslinking reactions, or can be made compatibilized with them, greatly expanding the range of applications. The next thing is also a theory was given. That is, introducing the correct type and amount of pendant functional groups. These saturated hydrocarbon polymers can be “painted” or coated. or these polymers can be coated and/or integrated with other materials. Composite materials with desirable combinations of properties layered or dispersed in these materials can be produced.

As already pointed out, the halogen functional group of benzyl undergoes an SN2 type nucleophilic substitution reaction. Therefore, it should constitute a highly active electrophile that can be converted into many other functional groups. Examples of these reactions can be found in the chemical literature.

It has been reported to selectively convert many functional groups in high yields, including the following: Contains: aldehyde, carboxy, amide, ether, ester, thioester, Thioether, alkoxy, cyanomethyl, hydroxymethyl, thiomethyl, a Minomethyl, cationic ionomer (quaternary ammonium or phosphonium, S -isothiouronium or sulfonium salts), anionic ionomers (sulfonium salts), anionic ionomers (sulfonium salts), nates, and carboxylate salts), etc. Furthermore, the literature describes benzyl halogen (bcirylic htlogea), triethanolamine, ethylene polymer Nuclear substitution with polyfunctional core molecules such as lyamine, malonate, etc. A number of examples are disclosed in which clusters of functional groups are substituted.

Almost all of this past research has focused on aromatic halomethyl (or benzyl) functional groups. This is the case for simple, minute (i.e., non-polymeric) molecules, including but, For chloromethylstyrene and polystyrene containing aromatic chloromethyl groups, other There are also many studies on nuclear substitution reactions for introducing functional groups. Much of this research For example, "Stylagel (slY>H1s)" containing various amounts of benzyl chlorine or involving reactions with lightly crosslinked polystyrene. Micromolecule containing benzyl chlorine The same nuclear substitution reaction that has already been reported for Styragel Altering the reaction conditions to promote the desired substitution reaction, which has been achieved many times. In particular, phase transfer catalysts (phlst+rs+++fe+ct js17st) was often necessary. in polystyrene Reactions involving benzyl chlorine are more difficult to achieve than reactions with simple micromolecules. Ru. This is because one of the reactants (the aromatic chloromethyl moiety) interacts with the other reactant. The close contact required between the reactants is non-existent when the reactants are in separate polymeric phases apart from the Because it's always difficult. In reactions involving benzyl chlorine in polystyrene The yields are also generally lower and side reactions are more prevalent. However, most The research was also on "Styragel", which preserves the solubility of polymers. For this reason, [Clean (CI!III) Generally, high conversions in reaction were not required. Chloromethylstyrene Recent good news regarding this research involving “Styragel” containing benzyl chlorine and Commentaries can be found in the literature. Marcel Ctsps (m’trcei Ctsps) and others “Chloromethylstyrene: Synthesis, Polymerization, and Transformation” Mation, Applicacons J ("Cklorame(hTls(Ile ne:5IIlthes)s.

Po17meriz*tion, Tnmslormtlion, Applic rlions’), Revueux Macromol, Dam. Physics (Rema.

M*c+omol, Chew, Ph7sics), C22(3), 343~ 40? Page (1982-83) and JMJ Frekerat (prtcbel), Chemical modification silicon ψ on polymers via phase transformer Far Catalysts in Crown Ethers and Phase Tigers Sphere O Catalyst Fist in Polymer Life Science, (ChmiCll) ModilicNion ol Potmers wit PhueTexn tle+ Ca1ilHts in Crova! 1hers tnd Ph 5seT+tuler C5HIH+t:n Po1y*er 5cieIl ce+), edited by Mattheus (MITthev@) and Kanetzker (Cue cher), published by Plenum Press, NY. 1984, and Je■-Pier+e Monteard (M oajbesrd) et al. "Romethylated φ Polystyrene" (Chemicals Ttmnslorms Eye out of Chloromej7111edFo17r17re++e’ ), J MS-Revieux Macromol.

Chem, Physics, (IMS-Rev, MIcroiol, Pkys,), □ C-28(3&4), pages 503-592 (198g).

Previous studies have shown that versatile, substantially saturated, pendant-functionalized In addition, a nuclear substitution reaction was carried out using isobutylene/isobutylene to produce a soluble copolymer. Applicable to C-methylstyrene/para-bromomethylstyrene terpolymer. do not have.

Summary of the invention In one embodiment, the present invention provides various lithographic materials comprising radiation-curable copolymers. Coating compositions suitable for use in roughy and corrosion protection applications It's a discovery. The term "radiation curable" refers to ultraviolet (UV), electron beam (E) B) Exposure of the copolymer to gamma rays, visible light, microwaves and similar radiation It means to vulcanize by. This radiation curable copo IJ mer has 4 Copolymers of isoolefins having from 7 to 7 carbon atoms and para-alkylstyrenes , wherein the radiation-reactive functional group is substituted on the para-alkyl group. good In a preferred embodiment, the isoolefin comprises isobutylene and para- The alkylstyrene may be para-methylstyrene and/or radiation-curable functionalized Contains para-methylstyrene. This copolymer can be prepared using UV or EB radiation. can be internally crosslinked and therefore do not require photoinitiators or crosslinking accelerators.

According to one embodiment of the invention, the radiation curable coating composition is Contains reactive functionalized copolymers. This radiation-reactive functionalized copo Limers include isoolefins and para-alkylstyrenes having 4 to 7 carbon atoms. The copolymer has a number average molecular weight (Mn) of about 5000 or more, and is preferably or about 5000 to about 5N, 000 or more, more preferably about 50,000 to about 300,000. Radiation-responsive functionalized copoly The polymer also preferably has a weight average molecular weight (Mw) to Mn ratio of about 6 or less. preferably, less than or equal to about 4 is more preferred, and less than or equal to about 2.5 is most preferred.

According to a preferred embodiment, the lithographic or corrosion inhibiting composition of the invention and/or or a preferred functionalized copolymer for use in the method is about 80 to 99.5 wt. % of isoolefins and about 15 to 20% of para-alkylstyrene by weight. an elastomeric, radiation-responsive functionalized copolymer comprising: The functionalized para-alkylstyrene is about 0.5% of para-alkylstyrene. It constitutes 55 mol%. However, vitreous or plastic materials may be manufactured as well. According to another embodiment, the radiation-responsive functionalized copolymer is about 10 to 99 ．． 5% by weight isoolefin, about 0.5 to 90% by weight para-alkyl styrene and about 0.5 to 55% by weight of a radiation-curable functionalized para-alkyl group. Contains tyrene.

Preferred embodiments of the lithographic or corrosion inhibiting compositions and/or methods of the present invention According to Contains para-alkylstyrene with a radiation-reactive functional group: -C-Y R' In the formula, R and R' are hydrogen, alkyl, and halogenated primary and secondary alkyl. and Y is an ether, ester, amine or another type of compound. radiation-reactive functional group(s) attached to the copolymer via a chemical bond; It is. These radiation-responsive functionalized copolymers are otherwise is the shape of the functional groups on the polymer backbone (i.e., those on the isoolefin carbons) Preferably, it is substantially free of other functional groups.

4 to 7 carbon atoms used in the preparation of the radiation-reactive functionalized copolymers described above. The precursor copolymer of isoolefin and para-alkylstyrene is an isoolefin. and para-alkylstyrene in a copolymerization reactor with a diluent and a Lewis acid. Mixing under copolymerization reaction conditions in the presence of a catalyst, and forming a complex with the catalyst or copolymerize with isoolefins or para-alkylstyrenes. manufactured by keeping certain impurities substantially free from the copolymerization reactor. will be built. This method was used to produce the radiation-reactive functionalized copolymers described above. A precursor copolymer is produced as a direct reaction product. And this thing is In the as-polymerized state, it has a substantially uniform composition distribution and also has a consists qualitatively of isoolefins and para-alkylstyrenes and about 5,000 have a higher number average molecular weight. This isobutylene/para-methylstyrene precursor Since the copolymer does not dissolve in the preferred diluent, the method is a slurry polymerization process. It is. However, isobutylene/para-methylstyrene precursor copolymer is the diluent. In another embodiment, a solution polymerization process is disclosed.

Precursor copolymers of inolefins and para-alkylstyrenes are then partially selective is brominated to produce a “base terpolymer” containing benzyl bromine functional groups. .

The base terpolymers include isoolefins having 4 to 7 carbon atoms and the following: Para-alkylstyrene represented by the formula: -C-1t R' One of the benzylic hydrogens of the copolymer consisting of bromine and the presence of a radical initiator Selective bromination of isoolefins and para-alkyl styrenes Manufactured by producing polymers. And this copolymer is para-alcoholic. After Kirstyrene: (+) or R' or as a mixture of (1) and (2), where R and R' are hydrogen, a independently selected from alkyl, and primary and secondary alkyl halides; The remer is otherwise substantially free of ring bromine or bromine on the polymer backbone. stomach. According to one embodiment of the selective bromination process, the radical initiator is photo- or thermally activated. be. According to another embodiment, the radical initiator has a half-life of about 5 to 2500 minutes. and preferably contains a bis-azo compound.

Convergence for benzylbromine, a highly active and versatile electrophile. Substitution of radiation-reactive functional groups is accomplished by nuclear substitution reactions, resulting in the desired radiation-responsiveness. A functional group and, if desired, - or more other functional groups are introduced.

For use in lithography or corrosion protection coatings and/or methods of the invention The pendant radiation-reactive functionalized copolymers are made of isoolefins and para- Radiation-responsive nuclear-substituted halogenated copolymers of alkylstyrenes This copolymer is characterized as a para-alkylstyrene with the following formula: or as a mixture of (1), (2), and/or (3) and/or (4). In the formula, R and R' are hydrogen, alkyl, preferably C8 to C2 alkyl. , and halogenated primary or secondary alkyl, preferably halogenated primary or secondary alkyl independently selected from the group S consisting of the second C4 to C2 alkyl, and X is chlorine. and bromine, preferably bromine, and Y is preferably base. Novel radiation reaction linked to polymers via single nuclear substitution of halogen 2 is an optional functional group which does not have to be radiation-reactive. - or multiple types of functional groups added, one of the /'% rogens of benzyl Represents something bound to a polymer via nuclear substitution.

According to another embodiment of the invention, lithography, corrosion protection, or other coatings may be used. The method of making a radiation-reactive coating comprises coating at least a portion of the surface of the article with the radiation-responsive coating described above. coating with a composition comprising a reamer and exposing said coating to electromagnetic radiation; exposure to radiation to introduce crosslinks therein. The method further includes an exposure step Selective penetration of radiation by forming a specific pattern of images on the coating before After the blocking step and the exposing step, the uncrosslinked coating is removed and the crosslinked developing the image formed as a coated coating. this The method further includes forming a patterned mask in the cross-linked coating. The step of etching the surface of the article after the removal step can be included.

In yet another embodiment of the invention, a radiation crosslinked coating composition is a cross-linking radiation reflector as described above, which is at least partially cross-linked by electromagnetic radiation. the functionalized composition. This crosslinked coating is used for printing elements and etching. anti-corrosion, solvent-resistant, anti-fracture, and other types of coatings. It is useful as a guideline.

Another embodiment of the present invention provides that the crosslinked coating composition of the present invention described above is It includes various articles including at least some of them.

Detailed description of the invention The coating composition is preferably a lithography, corrosion protection, or sealant. The coating composition as a coating includes one or more radiation-reactive functional groups. isobutylene/para-methylstyrene/para-bromomethyl functionalized with Contains Rustyrene-based terpolymer.

A, radiation-reactive copolymer The coating is an isoolefin containing para-alkylstyrene of the formula: Contains a radiation-reactive copolymer of carbon and para-alkylstyrene: R' In the formula, W includes at least Y, and optionally Y and one of hydrogen, X, and Z. may include mixtures with the above, provided that R, R', X, Y and 2 are as defined above. That's right. Radiation-reactive substituted para-alkylstyrenes (where W is Y) ) may constitute from about 0.5% to about 55% by weight of the functionalized copolymer, but less than about 0% ．． 5 to about 20% by weight is preferred, and about 0.5 to about 15% by weight is more preferred; About 1 to about 7% by weight is particularly preferred. Unsubstituted para-alkylstyrene (W is water) may constitute from about 0.5 to about 90% by weight of the functionalized copolymer. , from about 1 to about 20% by weight, and from about 2 to about 10% by weight is particularly preferred. stomach. Radically halogenated para-alkylstyrene (W is X) may constitute up to about 55% by weight of the copolymer, but preferably no more than about 20% by weight. more preferably about 15% by weight or less. In a preferred embodiment, halogen Para-alkyl styrenes can, for example, undergo nuclear substitution by Y and/or Z groups. more substantially completely converted and, as a result, the radiation-responsive copolymer is less halogenated. essentially free of para-alkylstyrene, preferably less than about 1% by weight; more preferably about 0.5% by weight or less, very preferably about 0.1% by weight or less , and especially up to about 0.02 mole % of halogenated para-alkylstyrenes. or not. Functionalized para-alkylstyrene (W is Z) may constitute 0 to about 55% by weight of the copolymer, preferably 0 to about 20% by weight. and more preferably from 0 to about 15% by weight. The remaining composition of the radiation-responsive copolymer Generally, from about 10 to about 99.5% by weight of the radiation-responsive copolymer, Preferably about 80 to about 99% by weight, more preferably about 90 to about 98% by weight % of isoolefins. The Mn of the radiation-reactive copolymer is approximately 500 0 to about 500.000, preferably about 50.000 to about 300.0 00, and most preferably from about 50,000 to about 150,000.

Radiation-reactive functional groups include various chemical groups that become reactive when irradiated with actinic radiation or electron beams. derived from compounds. These include photoinitiators from many different well-known classes , the photoinitiator is a nucleated group containing a benzyl halogen leaving group and a photoinitiator moiety. Isobutylene/para-methylstyrene/para- Can be incorporated into bromomethylstyrene-based terpolymers.

Typical photoinitiators include2 (Insects) Aromatic aldehydes and ketones, such as benzophenone, 4-chlorobenzene Nzophenone, 4-hydroxybenzophenone, benzoquinone, natsutaquinone, Anthraquinone, 2-chloroanthraquinone, benzylideneacetophenone, Cetophenone, propiophenone, cyclopropylphenyl ketone, benzal Dehyde, β-naphthylphenyl ketone, β-naphthaldehyde, β-acetona Futone, 2,3-pentanedione, benzyl (beoKil), fluorenone, Benzantrone, Michler's ketone , bis(parahydroxybenzylidene)acetone, benzoin, deoxybenzo such as in, chlorodeoxybenzoin and similar, (b) alkoxy and acyl substituted aromatic compounds, such as 2,2-dimethyloxy C-2-phenyl, 1,3.5-triacetylbenzene, 2,5-jetoxys such as tilbenes, and similar; (C) Heteroaromatic compounds, such as thioxanthone and the like. , (d) fused ring polycyclic aromatic compounds, such as anthracene, pyrene and the like; (e) N,N-disubstituted dithiocarbamates, (1) Conjugated unsaturated fats fatty acids, such as tung oil acid and their derivatives; (g1 α,β-unsaturated aromatic carboxylic acid represented by the following formula: Ar-(C=CH) *-(CToC■)b-COOH■ R1+ where R' is selected from the group consisting of H, CN, and NO2, and a and b are 0 or 1 and Ar is, for example, phenyl, m-nitrophenyl, p-chlorophenyl. phenyl, acetoxyphenyl, styryl, styryl phenyl, p-methoxyphenyl Nyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 2-furfuryl and 2- Aryl groups such as chenyl and, for example, hydrocarbyl, nitro , with one or more other groups such as chloro, alkoxy, azide and sulfone azide. (may be substituted) [Representative examples of these aromatic carboxylic acids include the following: Benzoic acid, cinnamic acid, m-nitrocinnamic acid, p-chlorocinnamic acid, p-methoxycinnamic acid Chalic acid, chxIcone, acrylic acid, p-phinyl bis(acrylic acid) acid), p-azidobenzoic acid, p-sulfoneazidobenzoic acid, α-cyanocinnamic acid Acid, cinnamylidene acetic acid, cinnamylidene malonic acid, α-cyanocinnamylidene Acetic acid, β-(11-naphthylacrylic acid, β-(2)-furfuryl-acrylic acid) , α-cyano-β-(2)-chenyl acrylic acid, β-(1) naphthylacrylic acid acids, β-(9)-anthryl acrylic acid and their esters and salts (e.g. , sodium benzoate) and similar].

(b) Nitroaromatic compounds, such as picramide, nitronaphthalene, 5-nitro Roacenaphthylene (nilroxcc-ngphhllenc), 2-nitro Fluorene and similar, such as (i) dye compounds, such as rose bengal, acridine orange, chlorophyll; Phosphorus, Crystalline Iolette, Eosin Y1 Fluorescein, Flavin Mononucleotide, hematoporphyrin, hemin, malachite green, methylene Blue, rhodamine B1 chlorophyll, cosine, eltro Syn(ertb+osiae), methylene green, toluidine blue, thioni and similar things, such as (j) Azide-containing compounds, such as azidobenzene, p-phenyl bisazide , p-azidobenzophenone, 4.4-diazidobenzophenone, 4.4'-di azidodiphenylmethane, 4.4'-diazidostilbene, 4.4'-diazide Chalcone, 3,6-di(4'-azidobenzal)cyclohexanone, 2,6-di (4'-azidobenzal)-4-methylcyclobexanone and similar (k) diazonium salt radical, e.g. p-diazodiphenylamine ・Rose formaldehyde condensate, l-diazo-4-dimethylaminobenzene Drofluoroborate, 1-diazo-3-methyl-4-dimethylaniline sulfate and (1) polyfunctionalizations containing photosensitive groups as described above. compounds, such as 1,2-naphthoquinone diazide, 2,3,4-trihydroxybenzene ndzophenone, bis-(naphthoquinone-1,2-diado-5-sulfonate), 2-(naphthoquinone-1,2-diazide-5-sulfonyloxy)-3-hydro Xinaphthalene, naphthoquinone-1,2-diazide-5-sulfonic acid Novolat Quester, ±butoquinone-1,2-diazide 5-sulfanilide, azide rest such as aromatic acid, azidophthalic acid, and the like, and (Il) Metal chelate compounds, such as benzenechromium tricarbonyl and similar Things, things like.

An extensive description of photoinitiators can be found in the Kuchitsuku publications of the Genren. child These compounds are generally halogenated isoolefins/para-alkyl styrene. Suitable reactive moieties for functionalizing ren-based terpolymers via nuclear substitution containing hydroxy or carboxyl groups or carboxylate salts or can be easily modified to incorporate suitable reactive moieties such as esters.

The performance of the coating as a lithographic or corrosion protection film is The content and type of linearly functionalized copolymer or copolymer blend and crosslinking Depends on bridge density. Crosslink density depends on radiation exposure and type of radiation-reactive copolymer. and is a direct function of concentration. The key variable in determining the type of functional group is the desired functionality. including the degree of oxidation and the wavelength of energy absorption. Photopolymer also contains additives and / or in the presence of another component included in the coating composition, including the extender. should generally exhibit a good crosslinking response when irradiated with

For example, cinnamate derivative photosensitive polymers have strong absorbance, so the irradiation energy is - absorbs well. Therefore, incorporating cinnamate as a UV-reactive functional group Coating systems that require higher UV radiation doses and shallower crosslinking depths is common. These systems are best suited for thin coatings and is particularly desirable in applications where crosslinking is limited to the outer shell or to the outer shell exposed to UV radiation. Delicious. On the contrary, PSA incorporating benzophenone has a weak absorbance. does not absorb much UV energy from And these are converted from photoexcited states to high water It has raw extraction reactivity. As a result, coatings containing benzophenone The system requires lower UV radiation doses and deeper crosslinking depths.

The selection of the type of functional group takes into account the wavelength of the radiation used to excite the functional group. It is also necessary to Those that are sensitive to UV wavelengths include cinnamates and benzophene. Contains non-, thioxanthone, anthraquinone, dithiocarbamate and similar It will be done. On the other hand, photosensitive polymers derived from naphthoquinone, for example, are sensitive to visible light. and tung oil acid derivatives can be used for high energy radiation such as gamma and electron beam radiation. - is an example of a polymer that can be crosslinked by radiation.

Coating performance, such as adhesion to various substrates, also depends on molecular weight, structure, and The composition of the polymer backbone, including both the concentration of para-methylstyrene and The degree to which the radiation-responsive copolymer is elastomeric (high in isobutylene, Tg The degree of thermoplasticity (high para-methyl styrene (high Tg)) Depends on.

Increasing the concentration of para-methylstyrene in the polymer backbone generally increases the overall Tg. therefore, it is a variable in the optimization.

Optimization of molecular structure, ie branched versus linear molecules, is also relevant. radiation Incorporating other functional groups within the curable coating system creates new variables and Greater control over polymer structure and optimization of its properties for a variety of different supports It's even bigger.

The route taken by radiation-reactive crosslinking depends on the type of functional group incorporated. for example , cinnamate derivative copolymers, e.g. cinnamoyl (φCf1=CIl- C(0) -) CU At the start of V, 2+2 light source additions will be performed.

Chain A Chain B ÷CtoC1l! Published--←C11-CHz-)-C[I2 Cl2 O〇 On the other hand, in benzoyl benzoate derivatives, free radical cross-linking under Uv exposure will be held. The incorporated benzophenone part is UV-radiated. The benzophenone functionalizes in a bonded state via a hydrogen abstraction mechanism that reacts with It is a photoinitiator known for generating free radicals in groups.

N,N-disubstituted dithiocarbamate derivatives also undergo radical crosslinking upon UV exposure. The bridge is done. Cross-linking occurs when the dithiocarbamate ester functional group is stable under irradiation. They tend to generate radicals and are therefore usually bundled in the case of polymers of isobutylene origin. This allows radical cross-linking and other radical chemical reactions rather than cleavage of the main chain. This is due to

Tung oil fatty acids are derived from tung oil, rich in eleostearic acid, and It is a fatty acid containing conjugated unsaturation. When exposed to electron beam irradiation, tung oil ester Crosslinking begins in copolymers functionalized with .

Copolymers functionalized with anthraquinone-2-carboxylate esters Contains the photoinitiator anthraquinone. Radical crosslinking is initiated by UV irradiation.

Other functional groups may optionally be present, and a number of functional groups, at least one is radiation-responsive) on a single functionalized pace copolymer containing or blend two or more functionalized copolymers together. You may. Adding functional groups can provide additional desirable properties to coating systems. Can be incorporated. For example, in addition to radiation-curable functional groups, amine functional groups The presence of water facilitates emulsification of radiation-curable lithographic coatings. become. Amine derivatives are also used in combination with benzophenone photoinitiators to provides easy protons.

As another example of mixing functional groups, one type of radiation-reactive functional group may be mixed with another type of radiation-reactive functional group. acts as an energy amplifier and transfer agent for the reactive groups, thus increasing the frequency Selected coatings for wider range and lower energy absorption can improve sensitivity. Photoexcitable acrolein present in coating composition Nictoleinium salt functional groups typically have high UV absorbance, low U energy for cinnamate groups with V transmittance and a narrow UV frequency photoinitiation range. Acts as a energy amplifier and transfer agent. By adding a photoexcitable functional group, the silicon Increasing cure depth and/or allowing thicker coatings with Ru.

Radiation-responsive copolymers contain one or more radiation-responsive functional groups and therefore The coating composition can be cured by radiation. Runs within the main chain of polyisobutylene Incorporating photoinitiators directly into the pendant para-methylstyrene groups dispersed in the dam The polymer can be directly cured by radiation. Furthermore, one or more A single derivatized copolymer or several types of copolymers with radiation-curable functional groups and other functional groups. Lithography or corrosion protection containing specific functional groups using blends of polymers The system is specially manufactured, whether it is classified as polar or non-polar. Adhesion to certain substrates can be enhanced. For example, the carboxylic acid functional group The presence of silane functional groups can enhance adhesion to aluminum, while silane functional groups can enhance adhesion to glass. can be improved. In addition, silane functional groups can be used in organosilicon polymer photoresist coatings. In semiconductor manufacturing processes that require Useful.

Those skilled in the art will typically incorporate many useful functional groups other than those mentioned above to create a lithographic design. The above discussion can be used to determine the implementation of the coating system for corrosion protection or corrosion protection. It is clear that the illustrative examples should not be considered limiting.

B. Other resin components Selective components of the lithographic or anticorrosive coating compositions of the present invention include: Tackifier suitable for use with UV or EB reactive copolymers. proper adhesion The imparting agent includes a resin that is compatible with the copolymer or copolymer blend. adhesive The imparting agent provides substantial adhesive strength, promotes wetting of the substrate, and For example, the adhesive performance of the cured composition may be improved to generally enhance the adhesive performance of the cured composition. Selected to optimize thermal performance.

Tackifiers are UV- or EB-reactive - or photosensitive polymers and gels. Generally, it should not substantially impede conversion performance.

Tackifier components suitable for use in the present invention include ESCOREZ or WINGT. Includes aliphatic or aromatic hydrocarbon resins such as ACK 95. WINGTAC K95 is a diene of piperylene and 2-methyl-2-butene with a softening point of 95°C. - is the trade name for the olefin copolymer. This resin contains 60% by weight Pipet Rylene, 10% by weight isoprene, 5% by weight cyclopentadiene, 15% by weight produced by cationic polymerization of 2-methylbutene and about 10% by weight of dimer. Ru. See US Patent No. 3.577,3911. The resinous copolymer is 2 0-80% by weight piperylene and 80-20% by weight 2-methyl-2-butene. Other tackifying resins of the same general type may be used, including. In the composition of the present invention Other adhesion-promoting resins that are also useful include hydrogenated rosins, rosin esters, and polyterpenes. These include polymers of esters, terpene phenolic resins, and mixed olefins. ES CORE Z 53gG and E CR-143H17) obtained under the trade name Preferred are hydrogenated hydrocarbon resins. This is because the unsaturation present in the tackifier is When the adhesive cures, it may be due to the absorption of radiant energy or because the tackifier is cross-linked. This is because it participates in the reaction and reduces the conversion of the polymer into a gel. these The ring and ball softening point of the tackifier generally ranges from about 10°C to about 180°C, preferably The temperature ranges from about 15°C to about 75°C. Under the product name ECR-Il+ and ECR-327 from Exxon Chemical Company (EIron Chuiul Co.) Other available hydrocarbon tackifiers have also been found to be particularly preferred. For example, E CR-143H resin is disclosed in U.S. Pat. No. 4.916.192, which is cited herein. By cationic polymerization of a C2 olefin/diolefin feed stream as shown Manufactured.

The properties of the PSA vary depending on the choice of tackifier resin.

Particularly important is the Tg of the tackifier. Optimization research shows that Adhesion-related properties, which are inversely proportional to normal crosslink density, optimize the Tg of PSA systems This can be improved by The choice of tackifier is an important variable in this regard. example For example, blend equal amounts of E CR-143H and E CR-111 tackifiers. Then, from the PSA system incorporating each individual tackifier resin, the blended tackifier resin PSA systems incorporating agents are superior in many adhesive properties. adhesive The general composition of the imparting agent is also an influential variable in optimizing the properties of the PSA. Yoshi Being an aromatic compound is advantageous for compatibility.

Other optional components of the coating compositions of the present invention are radiation-inactive polymers. and its addition does not interfere with the necessary radiation sensitivity. radiation Line inert *n=acts as a low cost 2,000 stent or other desired can be used to introduce functional groups.

C. Method of Preparation and Use of Coating Compositions Based on Embodiments of the Invention (Coating Compositions) The tackifier system optionally includes up to about 50 parts by weight of both the tackifier resin and the polymer. a non-radiation-reactive resin blended in an amount of 50 parts by weight or more of one or more radiation comprises a functionalized polymer containing radiation-reactive functional groups, where the weight of the radiation-reactive component The sum of parts and parts by weight of the non-radiation-reactive component is 100.

Other additives include antioxidants, non-polymeric inorganic or organic particulate fillers or reinforcements. materials, coupling agents, dyes or pigments, and other radiation crosslinking. May contain no additives.

The antioxidant or stabilizer is about 0.1 to about 3% by weight, preferably about 0.1 to about 3% by weight. about 1.5% by weight, more preferably about 0.1 to about 1% by weight, and typically Approximately 0.5% by weight can be added.

Particulate fillers that can be used for thickening and cost reduction include glass, silica, amorphous Including S　s　2, fumed alumina, calcium carbonate, fibers and similar products.

Suitable commercially available fillers include the trade names CAB-0-3I L, ZEO8I L3. 5. Available after AERO8I L R972, DUCRALID, etc. .

Suitable coupling agents include, for example, silane compounds, organotitanates, organosyl Organic golds such as konates, organozircoaluminates, chromium complexes and similar including (but not limited to) compounds of the genus. These are generally used for specific purposes. selected to promote adhesion based on the support and/or filler involved in the process. It will be done.

Suitable dyes include Fuchsine (C142SIO), Cs1cosidG r! e@5 (CI44090), 5olyent Yellow (CI4100 B), and the like. Suitable pigments include titanium dioxide, colloidal carbon, graphite, ceramic, clay, phosphor particles, and metal particles, e.g. Includes aluminum, magnetic iron, copper, and the like.

Coating compositions of the present invention optionally include copolymer emulsions and hot A solution of the radiation-reactive copolymer and other ingredients in an organic solvent, although a melt can also be used. Preferably, it is prepared as This coating composition is made from a solvent such as toluene. can be coated onto a support from a solution containing up to about 40% solids in the medium; The solvent is removed by evaporation prior to crosslinking by exposure to radiation. Or with another method to mix the ingredients in the solvent, emulsify the mixture, evaporate the solvent, and The adhesive is applied to the support as an emulsion of 50 to 60% solids by weight. Can be done. Prior to crosslinking, water is removed by evaporation using conventional drying equipment and techniques.

For hot melt use, the coating composition provides a uniform blend Radiation-responsive copolymers can be blended with other ingredients in the molten state up to Ru.

Various methods of blending materials of this type are known in the art. and uniform Any method that can produce a blend can be used. Typical blending equipment For example, a mixing extruder, a kneading roll machine, a Banbury mixer, a Brabender , etc. Generally speaking, the blend components mix easily in the molten state and A heating container equipped with a stirrer is sufficient. order of adding ingredients Although there is no specific method, generally the polymer resin is added first and then melted in a container. Heat until. Then add the optional ingredients.

Either the hot melt adhesive can be cooled and reheated at the time of use, or it can be from the receiver or melt pot using a pump or conventional equipment for pressure extrusion. It can be used directly by supplying it. An important feature of the invention is that The melt pot stability of the melt formulation is good, resulting in e.g. Under typical hot melt conditions such as temperatures between 140°C and 140°C, premature curing is almost impossible. It won't happen. In general, high viscosities such as 150.000cps are also generally acceptable. but sufficient for a target viscosity of approximately 100.000 cps heated. For suitable pot stability, the viscosity of the hot melt should be should not increase by more than 20% when maintained for 8 hours at a time.

Preparation of coated articles such as films, sheets, plates, and moldings At least a portion of the surface of the selected article is coated with a solution, emulsion of a radiation-reactive composition. This includes an initial step of coating with hot melt or hot melt coating. What suits It can also be used in coating methods, whereas applications involving composites Possible supports are paper and paperboard; fiberglass: wood; graphite; conductive metals, e.g. For example, copper, aluminum, zinc, and steel, etc.; and silicon arsenide or gallium arsenide. Semiconductor supports such as glass and ceramics; textiles, natural and synthetic woven fabrics or is non-woven fabric; ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, homopolymers and copolymers of styrene, isobutyne, and acrylonitrile. Synthetic resins containing; polyethylene terephthalate; polyamide; and cellulose acetate It can consist of cellulose esters such as tate and cellulose butyrate. Wear.

The latter polymeric support may be filled with fillers such as various synthetic, natural, or modified fibers or Reinforcements such as cotton, cellulose acetate, viscose rayon, and paper; and polyamide fibers.

These reinforced supports may be of laminated or composite form.

The radiation-responsive copolymer composition coating has a dry thickness of about 0.0 The coating ranges from 5 to about IO mils (nil). wet polymer co Drying of the coating may be done by air drying or by any other method preferred by the practitioner. This can be done by using certain drying methods. Radiation reactive coat Supports containing coatings can be stored for long periods of time before final use.

Suitable sources of actinic radiation used to carry out the crosslinking reaction are carbon arc, mercury vapor Includes arc and fluorescent solar lights. Electron beam radiation or high energy ionizing radiation , obtained from suitable sources such as: nuclear reactors, resonant transformer accelerators, Thief electron accelerator, Lintc electron accelerator, Pettertron, Synchro tron, cyclotron, or similar. Radiation from these sources includes electrons, Ionizing particles such as electrons, neutrons, deuterons, gamma rays, X-rays, α-particles, and β-particles Generate radiation.

Crosslinking is conveniently carried out at room temperature, but can be carried out at lower or higher temperatures if necessary. You can also do it. This prevents the crosslinking reaction from being inhibited by air and prevents the polymer from becoming acidic. The crosslinking reaction should be carried out in an inert atmosphere to prevent decomposition due to chemical reaction. are also within the spirit and scope of the invention.

The amount and type of radiation required depends primarily on the type and amount of radiation-sensitive functional groups used; It depends on the thickness of the coating and the level of curing desired. Appropriate dose of EB radiation from about 0.2 megarads to about 20 megarads, preferably from about 1 megarads to about 1 megarads. Including Megarad. A suitable UV radiation dose is from about 0.05 to about 21/at, preferably or about 0.1 to about IJ/d.

The resulting crosslinkable composition is suitable for lithography, corrosion protection, barrier, and high oil, Requires grease and solvent resistance as well as enhanced stiffness derived from the cross-linked matrix. It can be used in a wide range of applications, including other applications where it is essential. To be more specific, In optical copying processes such as photocopying, photochemical copying, lithography, and intaglio printing. ; using tools to create complex shapes and/or designs such as microelectronic circuits; Photoetching - resist mass, which is preferably engraved or etched without In processes requiring corrosion protection; as a corrosion protection film on metal; paper, paperboard water-, oil-, and/or solvent-resistant coatings for articles containing textiles, plastics, and rubber. As a shatterproof coating on glass; Caulk and sealer can be used as an agent; and in other ways.

Lithography generally refers to the process of transferring patterns between various media do. Lithographic coatings are generally used to project patterns of interest. A radiation-sensitive coating suitable for receiving an image.

Once projected, an image is formed that cannot be erased during coating. This projection The image to be captured may be a negative or a positive image of the target image. Typically, "projection" radiation The pattern's "transparency" (i" lnpstenc7) J is created. Revealing the coating through its transparency Upon exposure, areas of the image are selectively cross-linked, so that certain solvent developers (depending on the coating, the solubility may be greater or less than potash) Ru. The more soluble, i.e., uncrosslinked, areas are removed during the development process and are During coating, the image of the pattern remains as a less soluble cross-linked polymer. Ru.

Suitable developer solvents include perchloroethylene, methylene chloride, methylene dichloride, methylene Tyl ethyl ketone, n-propanol, toluene, benzene, ethyl acetate, and Water is included if applicable. Carefully select the solvent liquid used for this operation Must. Because solvent liquids are good solvents for unexposed areas. must have an effect on the insolubilized copolymer and support. This is because it should have almost no effect.

The developer solvent is coated for about 30 seconds to about 3 minutes, depending on the particular solvent used. should be kept in contact with the

The polymer coating developed in this way is then washed with fresh solvent. , dried.

The development process, especially in printing applications, involves etching the underlying support. Process of increasing the height of the image area in relief, removing uncrosslinked coatings and several different steps including changing the hydrophilic properties of the indicator. include.

The present invention allows cross-linked coatings to generally be placed on a raised printing surface on a plate. It has utility in photochemical copying processes where it remains as an element. The ink is dry-oiled. As in offset printing and regular letterpress printing, the raised part of the plate or on damaged areas such as intaglio printing, e.g. line and reverse mesh plates. Therefore, it is carried. The thickness of the radiation-responsive layer is the thickness desired in the relief image. is a direct function of the object being copied, especially the extent of the non-printing area do. Other examples of such uses include offset printing, silk screen printing, Copy pad (+Iuplict pxd), manifold stencil sheet Coating (mgnHold 5tencil shegl-iag co xting), lithographic printing plates, relief plates, gravure plates, photoengraving, collotype and and lithographic printing type element, magenta screen (migenlx 5crte++), Screen stencils, mesh plates and continuous colorable images, diazonium salts and carbon In a vapor development system containing a coupling agent, a wet type containing a color former and a coupling agent. Includes direct positive and negative systems that use development.

In the production of negative surface plates, coated plates are placed in a vacuum baking frame. and place the negative on it exactly. Close the frame and expose to a strong light source Pull it empty to bring the negative into close contact with the plate. Passes light through the transparent area of the negative Allow the coating on the plate to cure, then remove the plate from the frame and display it. Image.

In the production of strongly corroded litho plates (deep-etch 1lbo plug) Then expose the coating to light through the positive. Wash away uncrosslinked areas, but In this case, the function of the hardened area is not to act as a beam plate; to form a positive stencil, while the image areas are lightly etched. Filled with hard lacquer ζ.

Bimetallic plates mean that oil and water do not wet all metals with the same ease. Use the fruit. Lipophilic metals such as steel are used in the statues, and oleophilic metals such as chromium are Use water-based metal in non-image areas. The plate manufacturing method is It is similar to that used for etching, but the purpose of etching is to remove a thin layer of chromium to form an image. The idea is to leave bare copper exposed for use.

These lithographic coating compositions are compatible with chemical and other types of As a resist layer (i.e. photoresist) for performing etching or engraving operations. It is also useful. After transferring the pattern and removing the uncrosslinked coating, the crosslinked coating The etching process includes a mask for the etching process. Applications include the production of decorative plaques or to create decorative effects; patterns for automatic engraving machines, casting molds, cutting and punching. Relief maps for dies, name stamps, Braille, e.g. fast curing on film coating, television phosphor light binder, variable area soundtrack on film e.g. board and paper edging by dies made from radiation-sensitive coatings. Embossing and especially printed circuits, other plastic products and microchips Includes photoresists in the manufacture of.

In semiconductor manufacturing processes, for example, exposed and developed resist is As a mask backing for bidirectional dilatation of laid layers and/or semiconductor supports. Ru.

This etching is typically done chemically or by plasma, but is inert against these. Exposure and development by appropriate pattern of resist layer The image is similar to the method described above for manufacturing printing elements. Following anisotropic etching The resist layer is removed using an isotropic plasma or chemical method in which the masking polymer is not inert. Can be removed by targeted etching.

The radiation curable coating compositions of the present invention can be used to coat films, sheets, and other coatings. Can be easily formed into molded products and then exposed to visible light, ultraviolet light, or high energy - Exposure to active radiation, such as radiation, crosslinks the polymer, thereby Non-corrosive for use as corrosion-resistant, solvent-resistant, and other protective coatings. Can be made soluble and non-soluble.

The coating composition of the present invention can be applied to water, seawater, high pH and low pH liquids, and the like. in close contact with corrosive liquids or gases, including It is useful as a corrosion-resistant protective coating on a variety of metal surfaces. example linings of food and beverage containers; containers used in manufacturing plants, ships, and the like; Includes pipes, linings for miscellaneous equipment; anti-rust coatings for automobiles, etc. be caught.

Other useful coatings include uncrosslinked copolymers as film-forming binders. or the preparation of various coating and/or impregnating compositions for use on paper and textiles. They can be used as adhesives in construction, and after irradiation they are resistant to removal by heat or solvents. can be made resistant.

This copolymer is useful as a binder for nonwovens or webs. These are non-woven uniformly over the entire area of the web or in a predetermined pattern, e.g. regular or geometric Can be applied along intersecting combinations of straight or curved parallel lines in irregular rows . The impregnated nonwoven web is then exposed to, for example, actinic radiation to remove the polymers present. crosslinks the treated nonwoven web, thereby making it resistant to degradation by water or solvents. can provide more or less resistance.

As a web coating, the coating of the present invention is applied over the entire area of the web. to coat the web evenly and then pass it through a light filter or opaque screen. cross-linked in a predetermined pattern, thereby forming a polymer film in selected areas. Only the coating can be crosslinked. After screened exposure, unexposed parts of the coating can be removed.

In such a method, the coating of the present invention can be applied to a “wet wipe” (vtt wipe) J, manufactures disposable diapers and/or diaper cover cloths. It can be used to

By using filter screens, bonded diapers or diaper cover blocks can be removed. The degree of cross-linking in different regions of the loss can be selectively controlled, thereby making it possible to For example, the crotch area should be resistant to decomposition due to moisture, while the surrounding area should be It can be made dissolvable by soaking in water for 30 seconds to 2 minutes or so.

Furthermore, the coating composition of the present invention has a low viscosity and is compatible with sealants and caulks. It can be used as It can be cured as a shatter-resistant protective coating on articles.

D. Preparation of radiation-functionalized copolymers 1. Preparation of copolymer precursors The present invention relates to isoolefins and para-alkyl styrene under specific polymerization conditions. containing direct reaction products (i.e. in their as-polymerized state), and can be radiation-functionalized (brominated and nucleated) with an unexpectedly uniform compositional distribution. It is based in part on the discovery that precursor copolymers can be made (via substitution). So Therefore, by using the polymerization procedure described herein, coating compositions of the present invention can be prepared. The polymer backbone of the novel functionalized copolymer for use in products, i.e., the precursor copolymer can be manufactured. These copolymers, including radiation-responsive copolymers, When evaluated by permeation chromatography (GPC), narrow Molecular weight distribution and substantially uniform composition distribution, i.e. uniform composition over the entire range This was demonstrated. Stated another way, more than about 95% by weight of the precursor copolymer product The upper one is about 10% by weight of the average para-alkylstyrene content based on the entire composition. and preferably up to about 7% by weight of para-alkylstyrene; And preferably, about 97% or more of the copolymer product is based on the total composition. within about 10% by weight of the average para-alkylstyrene content, preferably about 7% by weight of the average para-alkylstyrene content. The para-alkylstyrene content is within %. In a highly preferred embodiment This is demonstrated by the following fact. That is, these functionalized Normalized differential refractive index (DRI) obtained by GPC of polymers and ultraviolet light ( UV) The curves most often overlap each other and merge into a substantially single curve.

This substantially homogeneous compositional uniformity is particularly relevant to the distribution among the compositions. That is, In the case of the precursor copolymer of the present invention, no matter what molecular weights are selected, the Percentage of para-alkylstyrene or isoolefin of para-alkylstyrene The ratios to ins will be substantially the same as described above. para-alkylstyrene Since the reactivity ratio between isoolefins such as isobutyne is close to 1.0, these The distribution of the copolymer within the composition will also be homogeneous. That is, these precursor copolymers are essentially random copolymers, with no pattern in any particular polymer chain. The units of alkylstyrene and isoolefin are essentially It will be randomly distributed.

The properties of these precursor copolymers offer many significant advantages over conventional ones. useful compounds having a number average molecular weight generally greater than about 5,000. It is also included that functionalized copolymers can be made. Coating of the present invention, Precursor copolymers useful for radiation-reactive functionalization in methods and articles has a number average molecular weight (Mn) of about 5000 to about 500. OOQ, preferably from about 50,000 to about 300,000, more preferably from about O5,00G to about 150,000 compositionally homogeneous copolymers. These products are relatively narrow It shows a narrow molecular weight distribution. In particular, these functionalized copolymers have an Mw/of about 6 or less. M indicates the n value, preferably about 4 or less, more preferably about 2.5 or less, and At the same time, these vary depending on the final intended use.

Thus, para-methylstyrene units are distributed throughout the precursor copolymer: -←CH2-CH-+~ In the formula, R and R' are hydrogen, alkyl, preferably C1 to C5 alkyl, and Halogenated primary and secondary alkyl, preferably C8 to C, halogenated alkyl independently selected from the group consisting of

Precursor copolymers used to functionalize radiation-sensitive copolymers by nucleophilic reactions Regarding the ratio of monomers used in the production of remer, this monomer ratio has a very wide range. It is a significant advantage of the present invention that it can be used in accordance with the present invention. Therefore, for example , about 10 to about 99.5% by weight, preferably about 80 to about 99% by weight, and Very preferably from about 90 to about 98% by weight isoolefin or isobutylene , and about 0.5 to about 90% by weight, preferably about 1 to about 20% by weight, and so on. more preferably about 2 to about 10% by weight para-alkylstyrene, preferably Precursor copolymers can be produced that actually contain para-methylstyrene. On the other hand, higher It is also possible to produce thermoplastics containing high concentrations of para-alkylstyrene. Therefore, the copolymer contains from about 10 to about 99.5% by weight isoolefin, preferably Preferably, isobutylene and about 0.5 to about 90% by weight, preferably about 1 to about 90% by weight. about 90% by weight para-alkylstyrene, preferably para-methylstyrene; include.

Isobutyne and para-methylstyrene readily copolymerize under cationic conditions.

This polymerization can be carried out using a Lewis acid catalyst. A suitable Lewis acid catalyst (free Dell-Krauff catalysts) also contain branched and gel-containing polymers with inferior properties. It has very little tendency to promote alkylation migration and side reactions that lead to crosslinking. This includes those showing good polymerization activity. Preferred catalysts include boron, aluminum aluminum, gallium, indium, titanium, zirconium, tin, vanadium, arsenic, Metals from groups Na, N and V of the periodic table of the elements, including antimony and bismuth It is a Lewis acid based on Strategy ■ Group a Lewis acids are represented by the general formula RmMXn (In the formula, M is a side group 1 metal, and R is alkyl or aryl of CI to C72. , alkylaryl, arylalkyl and cycloalkyl groups. m is a number from 0 to 3, and X is fluorine, salt A halogen independently selected from the group consisting of bromine, bromine, and iodine, and the sum of m and n is equal to 3). Examples include aluminum chloride, aluminum bromide, boron trifluoride , boron trichloride, ethylaluminum dichloride (El^1clx), diethyl Aluminum chloride (Et+^IcI), ethylaluminum sesquichloride Lido (E order, 5AICI+, s), trimethylaluminum, and triethyl Including, but not limited to, aluminum. Group Ⅰ Lewis acids have the general formula MX4 (M is a group II metal, X is a ligand, preferably a halogen) ). Examples include titanium tetrachloride, zirconium tetrachloride, or tin tetrachloride But it is not limited to this. Group V Lewis acids are represented by the general formula MX7, where M is is a Group V metal, X is a ligand, preferably a halogen, and y is an integer from 3 to 5). Examples include vanadium tetrachloride and antimony trifluoride. This includes, but is not limited to,

Preferred Lewis acid catalysts are used alone or in co-catalysts such as anhydrous HF or HCI. Brønsted acids, or halogens such as benzyl chloride or tert-butyl chloride. The most preferred catalyst is rather Catalysts that are classified as weak alkylation catalysts, therefore they are similar to the aforementioned catalysts. It is one of the weaker Lewis acids. Ethylaluminum dichloride, and preferred Alternatively, a mixture of ethylaluminum dichloride and diethylaluminum chloride These most preferred catalysts, such as It is not a catalyst. This is because, in the case of the present invention, as mentioned above, the conventional alkyl Indanyl ring formation is more likely to occur with catalysts commonly used to promote the reaction. This is because there is a strong desire to minimize side reactions such as. Usage amount of such catalyst depends on the desired molecular weight and molecular weight distribution of the copolymer being produced, but generally from about 20 ppm to about 1% by weight, based on the total amount of monomers to be polymerized; Preferably, from about G,01]1 to about O32% by weight.

Suitable diluents for monomers, catalyst components and polymer reaction products include common types of aliphatic and aromatic hydrocarbons used in or as mixtures; Mix with the hydrocarbon diluent in an amount up to approximately 100% by volume of the total diluent supplied to the reaction area. This includes C3 to C6 halogenated hydrocarbons used in monomer selected If it is soluble in the diluent, the catalyst need not necessarily be soluble in it either. is common.

This method can be carried out either in the form of a slurry of the resulting polymer in the diluent used or as a homogeneous solution. It can be done as a process. However, the lower viscosity mixture in the reactor slurry concentrations of up to about 40% by weight of polymer are possible. Therefore, it is preferable to adopt a slurry process. If the slurry concentration is high, More effective because less reactants and diluent must be recycled per polymer. Efficient processing is possible. For example, for a slurry concentration of 33%, the polymer Only 2 units of unreacted reactant and diluent need to be recycled per unit.

In any case, the amount of diluent fed to the reaction zone will depend on the process used and the production point. Depending on the molecular weight of the remer, the polymer concentration in the effluent leaving the reaction zone should be approximately 6 Sufficient to maintain less than 0% by weight, preferably within the range of about 5 to about 35% by weight. Must. Too high a polymer concentration may result in poor temperature control or rapid reaction. It is generally undesirable for a number of reasons, including reactor fouling and gel formation. Polymer - Too high a concentration will increase the concentration in the reactor and prevent proper mixing and effective heat transfer. Excessive power is required to secure the target. Such improper mixing and heat transfer effects This loss results in locally high monomer concentrations and inside the reactor, which eventually leads to fouling of the reactor surface. may lead to hot spots. However, diene-functional butyl rubber (e.g. isobutyne-isoprene copolymer), high polymer The tendency of the prior art to form gels at concentrations is substantially eliminated by the present invention using para-methylstyrene. In any case Typical examples of diluents that may be used alone or in mixtures are propane, butane, , pentane, cyclopentane, hexane, toluene, heptane, isooctane, Others, and books on methylene chloride, chloroform, carbon tetrachloride, methyl chloride, etc. Includes a variety of halohydrocarbon solvents that are particularly advantageous in the invention, and methyl chloride is particularly preferred.

Even if specific monomers are used (e.g. isobutyne and para-methylstyrene) slurry or solution as the composition distribution of the feeds varies between them. When the ratio of monomers used therein changes to maintain liquid polymerization, the copolymerization Different diluents may need to be used depending on their effect on the solubility of the remer. Either However, as mentioned above, there are important points in producing the copolymer precursor of the present invention. produces impurities, i.e. complexes with the catalyst if present, from the polymerization reactor. or polymerize with isoolefins or para-alkylstyrenes, and thus The molecular weight characteristics necessary for producing the copolymerization reactant before polymerization and the PSA or PSA of the present invention. excludes impurities that prevent the coating product from obtaining good physical properties. Is Rukoto. Otherwise, the substantially homogeneous compositional distribution and/or narrow Polymers with molecular weight distribution cannot be produced.

Of particular importance, these impurities include catalyst poisons, moisture, and e.g. Contains other undesirable copolymerizable monomers such as alkylstyrene and similar It is to do so. These impurities are not introduced into the system, and in the end, para-alkyl styrene is purity of about 95.0% by weight or more, preferably about 97.5% by weight or more, and to increase the purity of the isoolefin to about 99.5% by weight or more, preferably about 99.8% by weight. The amount should be at least %. The purity of the diluent used here is approximately 99.0% by weight or more. , preferably about 99.8% by weight or more.

Generally speaking, the polymerization reaction involves the use of para-methylstyrene and isobutyne as catalysts. in a polymerization reactor in the presence of a diluent (such as a Lewis acid catalyst) and a diluent. For low molecular weight polymers, the copolymerization conditions include temperatures below about 0°C, with stirring. mixing under conditions and means to remove the heat of polymerization to maintain the desired reaction temperature; This is done by giving In particular, the polymerization is carried out in an inert gas atmosphere and substantially in water. Under batch conditions of cationic polymerization, such as in the absence of It can be carried out. Polymerization is carried out using an effective stirring device such as a turbo mixer or propeller. stages, draft tubes, external cooling jackets, and internal cooling coils, or other means for removing polymerization heat, inlet pipes for monomer, catalyst and diluent, temperature detection means, storage baffled tank reaction with effluent overflow pipe connected to holding vessel or quench tank It is preferable to carry out the polymerization continuously using a typical continuous polymerization method using a vessel. reaction Purge the vessel of air and moisture and charge the reactor with a dry, purified solvent or mixture of solvents. The monomers and catalyst must then be introduced.

The reactor normally used for the polymerization of butyl rubber is used for the polymerization reaction of the copolymer intermediate of the present invention. Generally suitable for use.

These reactors are essentially large heat exchangers, and the contents of the reactor are Via a row of heat exchange tubes surrounded by boiling ethylene for heat removal. It is then rapidly transported via a central draft tube by efficient ship-shaped vanes. circulates. Catalyst and monomer are continuously fed into the reactor and mixed by a pump. It will be done. The reactor effluent flows into a steam heated flash tank.

The heat of polymerization can also be removed by a closed circuit equipped with pumps, within which the reactor The contents are continuously circulated via an external heat exchanger.

When conducting slurry polymerization processes, the reactor generally ranges from about -85°C to about -115°C. ℃, preferably from about -89°C to about -96°C. Solution polymerization and cement Suspension polymerization is operated at much higher temperatures, such as about -40°C, but the desired copolymer depending on the molecular weight of the catalyst and the particular catalyst system used. Therefore, acceptable solution polymerization The temperature range is from about -35°C to about -100°C, preferably from about -40°C to about - The temperature is 80°C.

The overall residence time depends on, for example, the activity and concentration of the catalyst, the 7mer concentration, the reaction temperature, and the desired molecular weight, but generally for about 1 minute to about 5 hours, preferably is about 10 minutes to about 60 minutes.

However, slurry polymerization processes typically cause the reactor to gradually become contaminated with polymer. As a result, the reactor must be periodically taken out of production for cleaning. So, with The dirt polymer is soluble so the reactor can be cleaned by solvent washing, and , it is very important to be able to return to driving. A deposit of insoluble gel polymer in the reactor. product is not acceptable. It is because solvent washing becomes ineffective and . The need to avoid such polymer gel build-up within the reactor is generally Used in the production of chill rubber (e.g. isobutylene/isoprene copolymers) This is one of the limiting factors on the amount of diene that can be produced.

The rose-methylstyrene/isobutyne copolymers of the present invention can also be used in solution polymerization processes. When manufactured by Para-methylstyrene is These new compounds do not have the severe molecular weight suppressing properties of ene. The polymerization temperature response to polymer molecular weight is more pronounced than for diene-functional copolymers. Because they are much flatter, higher molecular weight polymers behave better at much higher temperatures (i.e. In contrast, in the case of diene-functional butyl copolymers, the temperature is about -90°C or less; -40Tl:) Can be produced. Such high polymerization temperatures reduce polymer concentration and molecular The same amount results in a very low viscosity. To be more specific, in this case, these The solution polymerization is carried out at a temperature of about -35°C to about -100°C, preferably about -40°C to about -8°C. It is possible to carry out at a temperature of 0°C. For example, Mn is 25. Low molecules below No. When producing quantities of polymer according to the invention, the temperature may be as high as 0°C. or about +I for very low molecular weight polymers with Mn of about 500 to 1,000. You can even raise the O’C. In addition, rose-methylstyrene/isobutyne copolymer The molecular weight distribution of the polymer is much narrower than that of diene-functional butyl rubber, and this This also results in very low solution viscosities at a given number average molecular weight.

Solution polymerization is particularly suitable for the rose-methylstyrene/isobutyne copolymers of the present invention. , with further advantages. This is because the precursor copolymer undergoes post-polymerization chemical modification. This is because it is produced in a desirable solution state suitable for. In the agglomerated state (i.e., using an internal mixer, extruder, etc.) to halogenate the precursor polymer. , and it is also possible to graft a core molecule-containing part onto it (grxlj). However, most reactions have advantages in terms of mixing, heat transfer, removal of unwanted by-products, etc. is more easily achieved in a more controlled manner in polymer solutions.

The polymerization process can also be carried out in the form of a so-called "cement suspension" polymerization process.

Specifically, these are because the polymer is only slightly soluble in the diluent; is sufficiently soluble in the polymer that a second phase containing substantially all of the polymer is formed. However, the viscosity of the continuous phase, i.e., the diluent phase, is sufficiently low that the second phase, i.e., the polymer The polymerization reaction is carried out in a diluent chosen so that the mer-rich phase can be dispersed therein. Yes. One form of these cement suspension polymerizations involves adding The polymerization is carried out in a diluent whose lower critical solution temperature is lower than the reaction temperature.

The lower critical solution temperature is the temperature above which the polymer is no longer in the solvent. It is defined as the temperature at which the substance cannot be dissolved. Furthermore, according to these methods, polymer If the temperature of the solution and diluent increases, above that temperature the polymer will no longer dissolve. It is thought that the temperature reaches a temperature that cannot be reached. If kept at this temperature, separation of the two phases will occur. Generally, the lower part is a heavier, polymer-rich phase and the upper part is a heavier, polymer-rich phase. It is a lighter solvent-rich phase. Therefore, this phenomenon is similar to the conventional solution polymerization process mentioned above. It can be used to separate polymers from solutions in processes. Anyway, desirable To achieve a high two-phase "cement suspension", the light phase is used to maintain a low viscosity. is a very poor solvent for polymers, and the polymer-rich heavy phase is Enough solvent to separate and behave as a liquid and disperse within the lighter phase. It is necessary to contain A detailed description of such cement suspension methods can be found in the U.S. No. 3.932.371, the disclosure of which is incorporated herein by reference. It is incorporated.

2. Production of halogenated base terpolymer Polymer recovered in bulk and dissolved Polymers produced by liquid polymerization process (after continuous quenching and removal of residual monomers) Examples of post-polymerization chemical modification reactions that can be carried out for both are disclosed herein. for producing highly versatile benzylhalogen-functional copolymer components) rogenation (eg, radical bromination). Venge by radical halogenation The introduction of halogens is surprisingly easy and highly selective in nature; Since benzyl halogen has a wide range of uses, this reaction is very suitable as a reforming reaction. Delicious.

Functionalization reactions such as halogenation can be performed by any of the polymerization methods mentioned above. For the precursor rose-methylstyrene/isobutyne copolymer, a separate post-polymerization It is done as a process. and direct halogenation, and very preferably radical halogenation is the preferred reaction.

The copolymer product of the prepolymerization is deactivated with the catalyst prior to such halogenation. , and/or remove catalyst residues, remove residual unconverted monomers, and remove copolymer can be processed by an appropriate method to make it into a form convenient for the halogenation reaction. Generally desirable.

Deactivation of the catalyst in the reactor effluent is caused by the formation of small molecules when the effluent is warmed. To prevent the continuation of polymerization with the formation of terminal ends and/or the occurrence of decomposition and crosslinking reactions. almost always desirable. This deactivation can be accomplished by conventional methods. generally stated Then, the aluminum-based catalyst commonly used when producing the copolymer of the present invention If, and K1. If the catalyst efficiency is achieved, an independent catalyst removal step is not necessary. However, much of this residue is removed from traditional water-based finishing processes. is extracted into the aqueous phase.

Residual unconverted monomers in the precursor copolymer react during halogenation and form halogens. and generally produce undesirable by-products. Therefore, the unconverted top The presence of polymers makes it difficult to control and measure the amount of desired functional groups introduced into the copolymer. do. Therefore, unless the copolymer is polymerized at very high conversion, these It is usual to remove residual monomers. Unreacted isobutyne can be removed using various strips. It is so volatile that it can be easily removed by pinging, but it has a high boiling point of 170°C. methylstyrene is very difficult to remove. Therefore, para-methylstyrene polymerizes to a very high level, making its removal and/or recycling unnecessary or at least It is also advantageous to reduce the amount included.

The halogenation reaction itself can be carried out either in the aggregated phase of the precursor copolymer or in solution or in a microorganism. It can be performed on finely dispersed slurry. Bulk halogenation requires proper mixing properly designed presses to provide halogen and corrosive reaction by-products. This can be done using a brewer or other internal mixer. Bulk halogen by extruder For halogenation, residual unreacted para-methylstyrene is removed using conventional finishing operations. can be completely removed by the This has the advantage of eliminating the possibility of a reaction occurring. The disadvantage is that solution halogenation are much more expensive and require high horsepower reactors (i.e., extruders). The homogeneity is poor due to the fact that it is a liquid and the mixing, heat control, etc. are inferior to that of a solution. The halogenation reaction is carried out under conditions that are difficult to control. This kind of lumpy Details of the rogogenation method are disclosed in U.S. Pat. No. 4,548,995, and this document Incorporated by reference.

Solution halogenation is desirable because good mixing and control of halogenation conditions is achieved. halogenated by-products are easier to remove, and a wider range of halogenated products can be removed. This is advantageous in that an initiator can be used. The disadvantage is that the remaining residue before halogenation complex side effects, including the need to remove unreacted para-methylstyrene and solvent halogenation. the presence of reactions and dissolution steps when the copolymer is produced by non-solution polymerization methods; including solvent removal, cleaning and recycling. Suitable for such halogenation Solvents include low boiling hydrocarbons (C4-C7) and halogenated hydrocarbons.

Halogenation can also be added to the copolymer in a suitable diluent that is a poor solvent for the copolymer. It is also possible for the mer to be in the form of a fine slurry or cement suspension. this is advantageous from a viscosity point of view and allows a high solids content during halogenation, but The slurry or suspension is stable and does not agglomerate or form a coating on the reactor surface. It is necessary to have less tendency to create. The high-boiling point para-methylstyrene was replaced with conventional It is impractical to remove the solvent by distillation, and halogenation of the solvent must be completely avoided. When carrying out solution or slurry halogenation, it is difficult to The halogenation conditions should be selected to avoid halogenation of the diluent and the residual parameters should be It is very important to reduce tylstyrene to acceptable levels.

Because the main (pri+uB) reaction sites for halogenation are completely different, the precursor Halogenation of para-methylstyrene/isobutyne copolymer intermediate and isobutyne copolymer intermediate The halogenation of isoprene (butyl) rubber differs significantly. para-methylstyrene In ren/isobutyne copolymers, the intrachain (main chain) olefinic unsaturation is unaffected by para-methylstyrene, so the main reactive halogenated moiety position is the attached para-methylstyrene moiety, which is the Much less reactive than olefinic sites. Halogenation of common butyl rubber conditions [e.g., in hydrocarbon solvents at low temperatures (such as below about +80°C)] and a short contact time (such as less than about 10 minutes) in the dark, uncatalyzed reaction mixture. Therefore, halogenation of the para-methylstyrene copolymer cannot be detected. moreover, It is not possible to chlorinate para-methylstyrene copolymers in polar diluents. However, the chlorinated species produced are It is completely different from the case. Such chlorinated species Unlike chlorination at the polymer site, chlorine on the aromatic ring and polymer backbone is and preferred first chlorination of benzyl (pria+xr7bent71ic c hlo+1nxfioa).

In the case of halogenation of para-methylstyrene/isobutyne copolymers, the ring carbon Halogenation is possible, but the products are rather inert and unimportant. but , surprisingly, this para-methylstyrene/isobutyne copolymer has the aforementioned Excessive polymer degradation, cross-linking or other desired functionalization in high yields It has been found that it can be introduced under practical conditions without any side reactions. Ta.

The halogenation of this para-methylstyrene/isobutyne copolymer was specially selected. However, when carried out under reaction conditions, without catalyst, reactants and their initiators, the reaction is completely Either it does not occur, or it progresses through various routes, and therefore produces many types of halides. to be accomplished. Therefore, hydrocarbons with low dielectric constants such as hexane or cyclohexane solution of para-methylstyrene/isobutyne copolymer in solvent at 30-60°C. When chlorine or bromine is added in the dark for about 5 minutes, essentially no reaction occurs. on the other hand , the chlorination reaction in a more polar (higher dielectric constant) diluent such as methylene chloride. When allowed to undergo chlorination, it is clear that chlorination occurs by many different routes; Therefore, many types of chlorinated products are generated. These include Although some of the highly desirable benzylic primary chlorine is present, most of the No chlorinated substances.

Side chain halogenation of alkyl-substituted benzenes, contrary to nuclear substitution, is performed under ionic conditions. It is known that the halogenation of small molecules is carried out by radicals rather than by radicals. Ru.

Therefore, Friedel-Krach catalysts (or metal halogenation catalysts in general) avoidance of polar diluents, and avoidance of photochemical, thermal, or other radiation initiators. Such radical conditions, including the use of I don't know if I can say it's good. However, halogenation of polymers, especially Even small side reactions are extremely important, so if we follow the same route as in the case of these small molecules, It is also known that there is no limit to In addition, radical halide with simultaneous hydrogen substitution In the chlorogenation, the combined rose-methylstyrene within the copolymer component of the invention The yoisami hydrogen on the le moiety is more easily substituted than the secondary hydrogen, and the secondary hydrogen is the primary benzyl It is known that hydrogen is more easily substituted than hydrogen.

However, rather surprisingly, the combined rosettes within the copolymer components of the present invention - Radical bromination of the methylstyryl moiety is very specific and almost exclusively It has been found that the benzyl functionality can occur in It was brought out. Although the high specificity of the bromination reaction can be maintained over a wide range of reaction conditions, , factors promoting ionic reaction pathways (i.e., polar diluents, Friedel-Crafts) (fluorocatalysts, etc.) provided that they are avoided.

In this way, during the rose-methylstyrene/isobutyne copolymerization of the precursor of the present invention, In a hydrocarbon solvent such as pentane, hexane, or heptane, light, heat or a selected radical initiator (depending on conditions, i.e. at a particular temperature) A specific radical initiator must be chosen with the appropriate half-life for the conditions, and (generally, a long half-life is preferred at high halogenation temperatures). It is used as a promoter of carhalogenation, selectively brominated and almost exclusively via conversion with little or no chain cleavage and/or cross-linking. A benzyl bromine functional group can be generated. Without wishing to be bound by theory, bromination The reaction proceeds by a rapid chain reaction of radicals, and the chain reaction consists of bromine atoms and bonds. A hydrogen atom is extracted from the rose-methyl group of the rose-methylstyryl moiety. The benzyl radicals generated alternately become carriers. Therefore, the proposed mechanism is It includes the following stages:

(1) Okiya Btt-*28tl heat or light tR → 2t (R is the starting radical) Btz + 1-+ RBr + Br・L CH2・ Chz・ HzBr Either one of the radicals reacts with a radical scavenger in the system, or the radicals recombine or disintegrate. The reaction stops when it self-destructs due to the equalization reaction.

This reaction can be carried out photochemically or thermally (CH, sensitized) as shown in step (1) above. (with or without agents), can be initiated by the generation of bromine radicals, or can be Radical initiators react indiscriminately with bromine radicals or solvents or polymers ( In other words, it reacts selectively with bromine molecules, rather than by hydrogen abstraction. Good to have.

The cited sensitizer absorbs low-energy photons by itself, dissociates, and eventually , is a photochemical sensitizer that causes the dissociation of bromine, and is a photochemical sensitizer that causes the dissociation of bromine and substances such as iodine. include.

Therefore, an initiator with a half-life of about 0.5 to about 2500 minutes under the desired reaction conditions is used. and more preferably from about IO to about 300 minutes. opening used The amount of initiator typically varies from about 0.02 to about 0.3% by weight. favorable start The agents include azobisisobutyronitrile and azobis(2,4-dimethylvaleryl)nitrile. Bisazotizations such as tolyl, azobis(2-methylbutyro)nitrile and similar It is a compound. Other radical initiators can also be used, but the precursor copolymer or solvent Rather than reacting with bromine to generate alkyl radicals, it selectively reacts with bromine molecules. Using a radical initiator with relatively weak hydrogen abstraction that generates bromine radicals is preferable. Otherwise, the molecular weight of the copolymer will decrease and cross-linking will occur. Undesirable side reactions such as bridge formation are likely to be promoted.

The radical bromination reaction of the present invention is highly selective and almost exclusively desirable. generates a new benzyl bromine functional group. In fact, the only major A side reaction is the disubstitution of the para-methyl group to form the dibromo derivative; However, more than about 60% of the bound rose-methylstyryl moieties are monosubstituted. It won't happen until it's done. Therefore, approximately 60 moles of rose-methylstyrene content The desired amount of benzyl bromine functionality in the form of monopropylene is added to the copolymer of the invention, up to % It can be introduced to market. Furthermore, as mentioned above, rose methyl The content of tyrene can be varied. Therefore, functional groups can be introduced in a wide range.

Therefore, the halogenated copolymer component of the present invention can be used in subsequent reactions, e.g. It is very useful in applications. Promid releasing group (b+osidtlcgriB gtoap), the copolymer is functionalized using a radiation-sensitive nucleophile. can be improved.

During bromination, the above-mentioned termination reactions should be minimized, and side reactions due to termination should be minimized to ensure a long process. Allows rapid radical chain reactions to occur in time, producing more benzyl bromine with each initiation It is desirable to introduce it. Therefore, the purity of the reaction system is important and Keep the steady-state radical concentration low enough to avoid binding and possible cross-linking. Must have. Radical generation with secondary reactions (in the absence of bromine) continues. The reaction must be quenched as soon as the bromine is consumed to avoid continuation. rapid cooling cooling, blocking the light source, adding dilute caustic, adding radical scavengers, or a combination thereof. This can be achieved by combining.

1 per mole of bromine that reacts with or replaces the attached para-methylstyryl moiety. Since moles of HBr are formed, it may participate in undesired side reactions or vice versa. This H is removed during the reaction or at least during polymer recovery so as not to catalyze the reaction. It is also desirable to neutralize or otherwise remove Br. In such a situation The addition or removal is typically a post-reaction caustic wash using a molar excess of caustic to HBr. This can be achieved by Alternatively, neutralization can be carried out using fine particles such as calcium carbonate powder. When a child base (which does not react much with bromine) is present in a dispersed state during the bromination reaction, HB This can be achieved by absorbing r as soon as it is generated.

Removal of HBr is performed using an inert gas (e.g. N2), preferably at elevated temperatures. This can also be achieved by stripping.

Brominated, quenched and neutralized vara-methylstyrene of the invention/ The “base terpolymer” of the isobutyne copolymer is recovered and treated with the appropriate stabilizer. finished by conventional methods including the addition of UV or other radiation-reactive functional groups. Highly desirable and useful in subsequent nuclear substitution reactions to incorporate to produce a saturated copolymer functionalized with a wide range of residual groups.

In particular, since only a small amount of tertiary benzyl bromine is produced in the copolymer molecule, Here, there is almost no possibility of dehydrohalogenation reaction. For this reason, a stable hardware A rogogenated polymer is produced. Furthermore, the presence of bromine on the ring methyl group makes this formation It confers many other important advantages on objects. Because this bromine is present, the area Functionalization by substitution with other functional groups is possible.

3. Nuclear substitution of base terpolymer Based on the benzyl bromine (halogen) functional group, the lithographic use of the present invention or a versatile functionalized saturated coating composition for corrosion protection coating compositions. It is highly suitable to produce polymers. This is because this functional group can be used in a wide range of can be used for selective nucleophilic substitution with the surrounding core molecules, thus allowing the desired type and amount of most of the functional groups of the pendant without undesirable side reactions and Degradation and/or cross-linking of the backbone of saturated copolymers containing benzidyl halogen functional groups This is because it can be introduced under conditions that are mild enough to avoid bridges. In addition, many In many cases, the pendant benzyl halogen is partially converted to another desired functional group. convert and retain the remainder, or later remove some of the remaining benzyl halogen functionality. can be converted to other new functional groups to produce copolymers containing mixed functional groups. mixture The functional groups can be grafted via one functional group to another functional polymer; It can also be cross-linked via another functional group or in contact with a surface! If you let me- ・It is advantageous to provide a unique combination of properties, such as:

Radically halogenated isobutylene/para-methylstyrene copolymer , an ``ideal'' method for producing various radiation-reactive functionalized saturated copolymers. It is a ``base copolymer'', but the characteristics of the benzyl halogen functional group that is its origin are One of the characteristics is that this benzyl halogen functional group undergoes a wide range of nuclear substitution reactions. , and that the conditions for these nuclear substitution reactions to proceed are relatively relaxed. benzil Halogen functional groups are highly reactive molecules that can react under appropriate conditions with nuclear molecules that can donate electrons. It is composed of electrophilic substances with high activity. Suitable nuclear materials include oxygen, sulfur, nitrogen, phosphorus, carbon, silicon, and especially magnesium, lithium, sodium, and potassium. This includes nuclear materials containing various metals, including um. Suitable UV-reactive nuclear materials include , e.g. 07 reactive carboxylate ester, dithiocarbamate ester and the like. The type of nuclear molecule that reacts with the benzyl halogen functional group is Just as importantly, these nuclear substitution reactions occur under relatively mild conditions. As a result, isobutylene/rose-methylstyrene copolymer The saturated backbone of the remer allows for the desired new release without cleavage or cross-linking reactions involving the saturated backbone. Substitution reactions for introducing new functional groups can be carried out to completion.

Another property of the benzylhalogen functionality is that the desired substitution reaction is accompanied by undesired side reactions. It is the selectivity that allows one to proceed without any. Benzylhalogen functionality is complex It undergoes a clean substitution reaction that does not involve an elimination reaction. Coupling Even if the side reaction leading to (coipliB) is only a small amount, it will lead to gelation. , this property is important in reactions involving soluble high molecular weight polymers.

In reactions involving simple molecules (usually - functional), only a small fraction of the desired product is produced. Even with a yield of 70%, purification and separation of undesired products is relatively easy. It is acceptable. Any involving already cross-linked polymers (e.g. “styragel”) In reactions where the starting polymer is already insoluble, low yields for the desired product can also be caused It is acceptable because it is sexual. However, the present invention, which contains many functional groups per molecule, In the reaction of soluble polymers, it is necessary to maintain solubility during reaction and recovery. Therefore, it is necessary to achieve 99% or more of the desired substitution reaction. slight (other reactions) ) a negligible amount of gel-forming side reactions hinder its usefulness. moreover , it is usually very difficult to purify substituted polymers and remove harmful by-products, or Or it is impossible. For this reason, the benzylhalogen functionality can be extracted under controlled conditions. It is important to be able to achieve high-yield nuclear substitution reactions in a selective single route using . Isobutylene/para-methylstyrene as “base” polymer for modification The use of chlorine/para-bromomethylstyrene and Containing useful pendant functional groups by performing a nuclear substitution reaction under controlled conditions A soluble, backbone saturated copolymer was prepared. Examples include: Ru: (1) Esters (acetate, stearate, lylt, eleostearate, many esters, including cinnamate, etc.) (2) hydrothousyl (directly bonded in place of benzyl halogen or another (3) carboxy, (4) Nitrile, (5) quaternary ammonium salt, (6) Quaternary phosphonium salt (7) S-isothiuronium salt (8) Dithiocarboxylate ester (9) Mercaptan (lO) carboxylate esters and ferulates, benzoylben Zoates, cinnamates, tung oil fatty acid esters, and anthraquinone-2-carbon containing a radiation-reactive functional group, as exemplified by ruboxylate, and (11) UV-reactive dithiocarbamate ester.

Isobutylene/para-methylstyrene/para-bromomethylstyrene terpolymer Generally, reactive derivatives, specifically reactive derivatives, which can be produced by nuclear substitution reactions against Although not all of the radiation-reactive derivatives have been manufactured, those skilled in the art will appreciate that the radiation-responsive derivatives are Most of the desired pendant functional groups include functional groups and mixtures of functional groups with clearly can be combined to suit a variety of purposes using the principles disclosed herein. That's it. Radiation crosslinking and emulsifying properties due to the combination of two or more different types of functional groups and/or can produce polymers with excellent adhesion to certain substrates. However, it is important that each of these properties can be brought out by judicious selection of the appropriate functional groups. This is the time when

Inventive versatile, pendant, radiation-sensitive, backbone saturated, soluble The “top priority” requirements for producing polymers via selective nucleophilic substitution reactions is as follows: (1) Isobutylene/para-halomethylstyrene/para-methylstyrene base Use of terpolymers for claimed nuclear substitution under appropriate, controlled conditions. Tar The composition of the polymer can be modified as needed to improve the properties (i.e. Tg1 hardness, flexibility, desired combinations of impact strength, level of functionality, etc.).

(2) Benzyl halogen with nucleophile and reaction medium attached to base terpolymer be chosen so that close contact between the material and the nuclear material can be achieved. In some cases, this contact uses different solvents, i.e., reaction media, for the polymer and the core molecule, and the reaction We also recognize that this can be achieved by employing appropriate phase transfer catalysts to promote Should.

(3) At the reaction site so that the desired nuclear substitution reaction is promoted under mild conditions. to achieve specific solvation.

(4) Loss of reaction specificity and make side reactions a serious problem, and/or crosslinking or “aggressive” or “hard” bases or high temperatures that cause decomposition reactions. Avoid "harsh" reactants or reaction conditions.

(5) The desired substitution reaction occurs rapidly under mild conditions, resulting in undesirable side reactions. nuclear reactants and promoters should be chosen properly to avoid the possibility of For example, isobu Tyrene/para-methylstyrene/para-bromomethylstyrene "base" tarpo The carboxylic acid nucleus in the esterification reaction to replace the benzyl bromine in the remer. When using substances, “hard” ionic salts of carboxylic acids are used as nuclear reactants. rather than using potassium salts of carboxylic acids as nuclear reactants at the same time. Select 18 crown-6 to solvate the ions and the desired esthetics. or tetrabutylammonium in a suitable solvent capable of promoting the substitution reaction. The counterion could be chosen as a sensitive "soft" acid to facilitate the reaction.

(6) The nuclear substitution reaction itself binds to the main chain of the base polymer. The ability to form pendant nuclear reactants in a state of The body sequentially nuclearally removes other unreacted benzylic bromines on the base terpolymer. As a result, the desired already attached new functional group is consumed while the desired Minimize sequential reactions by recognizing that undesirable crosslinking and gelation will occur. Choose reaction conditions that will

Therefore, the reaction conditions are such that the unreacted nuclear reactants used in the claimed nuclear substitution reaction are a stronger or more reactive nuclear molecule or produced by a substitution reaction Reaction conditions must be chosen such that the attached nuclear functionality is present in significant excess. do not have. For example, a bound basic group can react with benzyl bromine under basic conditions. It must be recognized that it becomes a core part that can react further. These polymers The group within - can react with other benzylic bromines, resulting in already bonded pendant functional groups are consumed and undesirable crosslinks form.

The result is a gelled polymer rather than the desired pendant functionalized polymer of the present invention. It's Rimmer. The benzyl bromine of the base terpolymer of the present invention is replaced by a mercaptan group. In an attempt to replace the bonded SH (mercaptan) group, the bonded SH (mercaptan) group is exposed to basic conditions. to form incorporated claim nuclear reactants, and these incorporated members The rucaptide group reacts with other benzyl bromines, resulting in an already incorporated pendyl bromine. The mercaptan functional group is consumed and an undesired thioether crosslink is formed, To produce a gelled polymer rather than the desired pendant functionalized polymer of the present invention. We must recognize that.

Similarly, when making the pendant hydroxy-functionalized polymers of the present invention, the attached The hydroxyl group of forms a claimed nuclear reactant in strongly basic conditions, and These attached alkoxide groups are sequentially attached to other unreacted groups of the base terpolymer. reacts with benzylic bromine, resulting in the already bonded pendant hydroxy functionality. groups are consumed and ether crosslinks are formed, resulting in the desired pendant functionalized polymer of the present invention. It must be recognized that this produces a rather gelled polymer.

The overriding requirement is to recognize the possibility of sequential reactions and choose conditions that minimize them. Radiation-reactive functionalization of pendants of the present invention with mixed pendant functional groups This is particularly important if the production of polymers is desired. These mixed functional polymers In order to protect the desired functional groups and avoid sequential reactions, the functional groups and It is extremely important to choose the right subject.

A polymer made of isoolefin and para-alkylstyrene-silane derivative polymer. The remer is a (N,N-dimethyl-3-aminopropyl)silane as shown below. Alternatives that can be readily prepared by nuclear substitution through the use of suitable nuclear silane reactants such as Representing a group of substances with wide applications: 11 CH3 HzBr RI ClI2 In the formula, R,, R2 and R3 are each independently hydrogen, chloro, methoxy, ethoxy, selected from the group consisting of alkoxy having 1 to about 5 carbon atoms, such as . The reactivity of these derivatives can vary depending on the number of silane species present and the Kashihara .

Polymer of isoolefin and para-alkylstyrene containing Si-CI bond is most reactive towards various types of nuclear materials, including weak nuclear molecules such as water. that Therefore, these materials can be vulcanized by exposure to the atmosphere and are therefore used as room temperature vulcanizable compositions (RT V) is very useful.

Similarly, these two that contain 5i-0 (alkyl) bonds also contain water! of It is reactive with nuclear molecules (although not as reactive as Si-CI). This reaction above properties are active in RTV applications, especially when release of neutral species during vulcanization is preferred. used. Proper uses of this silane material include sealants and adhesives, where , the silane functionality enables crosslinking and adhesion to supports such as glass. Improved.

Isoolefins and para-alkylstyrene-silane derivatives containing 5i-H bonds These polymers have unique reactivity. These are subject to three basic types of reactions. Ru.

These in the presence of tin octoate, zinc octoate, and other metal salts Reacts with hydroxyl or silanol functionalized materials to create bonds and generate hydrogen. Ru. This reaction can be used to impart hydrophobic properties to glass, leather, paper or textile surfaces. .

S i-H functional groups can be converted into olefins in the presence of certain free radicals or noble metal catalysts. reacts. This reaction opens up applications for addition curing (RTV) or low temperature vulcanization. be. These polymers such as polybutadiene or vinyl functional silicones Blends with other olefin-containing polymers include isoolefins and para-alkyl Rapidly generates an intermolecular crosslinking system between a styrene-containing polymer and another polymer.

Polymers containing isoolefins and para-alkylstyrene-vinyl silicone systems - provides a useful heat-stable cross-linked woven fabric with greater permeability than existing silicone systems do.

These 5i-H polymers consisting of isoolefins and para-alkylstyrene derivatives A third useful reaction for remers is as a reducing agent for polymeric types. S i -H The compound is active against nitroaromatics, acid chlorides, aldehydes and ketones. , known as a mild, selective reducing agent.

Attaching these reactants to polymers offers the advantage of easier separation; The polymer is easily separated from the lower molecular weight reduced species and isolated (iso There is no need to hydrolyze the remaining reactants prior to lstin). Another advantage is that These reductions are compatible with a wide range of solvents including hexane, methylene chloride and dioxane. This can be done in the presence of air and moisture in the system.

“Including isobutylene/para-methylstyrene and para-bromomethylstyrene” The novel invention derived via selective nucleophilic substitution reaction of base' terpolymers A wide range of pendant functionalized, backbone saturated, soluble copolymers of are further disclosed in the Examples, addressing specific pendant functional groups.

These examples demonstrate that para-methyl isobutylene-rich low Tg elastomers up to high Tg plastics, which are abundant in Covers a wide range of properties including tough high impact compositions. The right pendant sensuality The presence of this group makes this whole range of products suitable for exterior applications such as automobiles and electrical appliances. Can be painted and adhesive or coated onto other substrates. The excellent environmental resistance of copolymers with saturated backbones allows them to be used as Can be used for external applications where this is an advantage. Additionally, these compositions contain appropriate functional groups. Reacts with or assists other functional polymers or fillers or fibers Composite structures (i.e. laminates) with desirable combinations of properties , dispersion, etc.).

In accordance with the present invention, a novel pendant radiation-responsive feature as disclosed and exemplified herein is disclosed. Energized saturated copolymers first have one or more electrophilic moieties attached to pendants. producing a base terpolymer comprising a saturated hydrocarbon backbone, then 1. Pe The desired, new By attaching new radiation-reactive functional groups, it can be manufactured easily and practically. It turned out that it is possible. When making the pendant functionalized copolymer component of the present invention, An electrophilic moiety attached to a pendant that is substituted with another functional group via a nucleophilic substitution reaction It is clear that the benzyl halogen moiety is desirable and important. Became. The electrophilic benzyl halogen moieties attached to these pendants are Random isobutylene/para-methylstyrene by the radical halogenation described above. Easily inserted into copolymers, isobutylene/para-methylstyrene/and bromine A base terpolymer consisting of random units containing chlorinated para-methylstyrene was produced. to be accomplished. This base terpolymer containing an electrophilic benzyl halogen moiety is ``parent polymer'' from which the novel pendant functionalized saturated copolymer of the present invention Polymers are produced via selective nucleophilic substitution reactions.

These novel, pendant functionalized polymers of the present invention “le+”)” unit: 1) linked isobutylene unit CH2 -C[I! -C- Hz b) linked p-alkylstyrene unit -C-11 R' C) attached brominated p-alkyl-styrene units (electrophilic moieties) -C-X R' d) a bonded pendant radiation-reactive functional group, a nucleus for benzyl halogen; -C-Y produced by substitution ■ R' e) non-radiation-reactive functional group of the attached pendant, to the benzyl halogen -C-2 produced by nuclear substitution R' In the formula, R and R' are hydrogen, alkyl, and halogenated primary and secondary alkyl. X is a halogen atom (preferably bromine and chlorine, bromine is the most preferred), and Y is bonded via one benzylhalogen nuclear substitution. The new bonded to the polymer such that the "mer" unit C becomes the "mer" unit d. 2 represents a radiation-reactive group, and 2 is formed via nuclear substitution of one benzyl halogen. The "mer" unit C bound to the polymer is bound to the polymer so that it becomes the "mer" unit e. Represents a new non-radiation-reactive group. In practice, when introducing mixed functional groups, There may be several different Y's and/or two's within the mer. Y and 2 are Penzilha When a nuclear reactant capable of donating electrons to the lid reacts with the base terpolymer according to the invention In place of the halogen in the “mer” unit C that was bonded to the polymer, It is what remains.

Four types (more if several different Y and/or difunctional groups are present) "Mer" units are randomly combined to form novel pendants in the compositions of the present invention. to produce a radiation-reactive functionalized backbone saturated polymer component.

The number average molecular weight of the entire polymer can vary from <SOO to> 100, ooO. Wear. The amount of each type of "mer" can be varied as follows: I) (imbutylene) "mer" unit about 10 to about 99.5% by weight, b) (p-alkylstyrene) "mer" units about 0.5 to about 90% by weight, cl (radical brominated p-alkyl styrene) "mer" unit approximately 0~ up to about 55% by weight, d) (the pendant is a radiation-reactive functional p-alkyl styrene) Len) “mer” unit about 0.5 to about 55% by weight, e) (If the pendant is non-radiating linearly reactive functional p-alkylstyrene) “mer” units from about 0 to about 55% by weight .

In practice, when introducing mixed functional groups, several different types of Y and/or two types of the same Present within the polymer. 2 for Y and U x is a nuclear reaction that can donate electrons to pendylhalide. When the reactant reacts with the base terpolymer according to the invention, the polyurethane is used instead of the halogen. and more preferably about 10 to about 99.5% by weight of I). preferably about 80 to about 99% by weight, and most preferably about 90 to about 98% by weight. % by weight, b) from about 0.5 to about 90% by weight, more preferably from about 1 to about 20% by weight %, and most preferably from about 2 to about 10% by weight, d) from about 0.5 to about 55 % by weight, more preferably from about 0.5 to about 20% by weight, and most preferably, about 0.5 to about 15 mol%, C) about 0 to about 55% by weight, more preferably about 0 to about 20% by weight, and most preferably about 0 to about 15% by weight, and C ) is about 0 to about 55% by weight, more preferably about 0 to about 20% by weight, and most preferably about 0 to about 20% by weight. Also preferably from about 0 to about 15% by weight. Number average of functionalized polymers The molecular mass ranges from about SON to about 500,000. More preferably about 50,000 to about 300,000, and most preferably about 50,000 to about 150,000 be.

According to one embodiment of the invention, the pendyl halide is endowed with electrons and the claimed nucleus The halide is removed via a substitution reaction and the radiation-reactive functional group Y and the desired The non-radiation-reactive functional group 2 is bonded to the benzyl position from which the halogen is removed. Nuclear reactants that can be expressed as Y or YM or 2 or ZM (wherein M is hydrogen, metal ion or ammonium ion, and Y and/or 2 are A simple nuclear molecule containing oxygen, sulfur, silicon, carbon, nitrogen, phosphorus or various metals, or Y and/or 2 are small molecules with a molecular weight <1000 and are suitable for the claimed nuclear substitution reaction. even if they contain other functional groups in addition to a simple core molecule that binds to the benzyl position. It is a good small molecule).

An oxygen-containing compound that brings about a -0- bond at the removed benzyl position of the halito ion. Examples of simple nuclear materials include, but are not limited to: - 803S sulfonate in oil alkoxide or phenoxide What to do.

A sulfur-containing compound that brings about a -8- bond at the removed benzyl position of the halito ion. Examples of simple nuclear materials include (but are not limited to) the following: In thiolate and thioferlate -3b Thioether In 13CN thiocyanate.

Silicon is added to bring about a -Si- bond at the benzyl position from which the halito ion is removed. Examples of simple nuclear materials with n = 1.2, or 3 include (but , but not limited to): 1l-5ib in silane In H-3ilIIR3-1 halosilane.

A carbon-containing compound that brings about a -C- bond at the removed benzyl position of the halito ion. Examples of simple nuclear materials include (but are not limited to): In cyanamide -C1h Organolithium (or other alkali or alkaline earth metal) compound in things HC-(R)-(CO2R12 malonate and generally placed under basic conditions) The substituent activates the carbon of methane. and carry out carbon alkylation reaction. di- or tri-substituted methane derivatives What to do.

A nitrogen-containing compound that brings about an -N- bond at the removed benzyl position of the halito ion. Examples of simple nuclear materials where n=1.2, or 3 include (but (including but not limited to): ) IN-C-R amide Yam NN11ds-In various amines 0 In maleimide Xi blasphemy The functional group of the species -N=C・0 in cyanate.

Contains phosphorus, resulting in a -P- bond at the removed benzyl position of the halito ion , n=1.2, or 3 include (but this (including but not limited to): P[lffiRa-m in various phosphines.

A metal-containing compound that brings about a -M- bond at the removed benzyl position of the halito ion. Examples of simple nuclear materials include (but are not limited to): Mg-( anthracene complex in THF) Li- (appropriately complexed) Y and/or Z are small molecules with a molecular weight of <1000, and are suitable for nucleophilic substitution reactions. In addition to a simple core moiety bound to the removed benzyl position of the halide ion, Examples of small molecules that also contain other functional groups include (but are not limited to): b) Nitriethanolamine, iminodiacetic acid, iminodiacetonitrile, imino Diethanol, vinylpyridine, cinnamate, eleostearate, lylua acrylate, benzoyl benzoate, penzoyl felt, dihydro xybenzophenone, crown ether derivatives, cryptand derivatives, cellulose sugar derivatives, low molecular weight polyethylene oxide chains with terminal nuclear groups, is a polypropylene oxide chain, etc. Y and/or 2 are for removal of halito ions Conditions involving other functional groups in addition to the simple nuclear material attached to the benzyl position These reactions carried out in greatly expands the type and range of functional groups that can be incorporated into pendant functionalized saturated polymers. It should be noted that it expands. This multifunctional Y and/or Z group is bonded ability to achieve desired results in various dispersants (i.e., lubricant dispersants). It is possible to combine clusters of polar groups, which is not easily achieved by nuclear substitution reactions. Functional groups (such as olefins or conjugated unsaturated) can be attached; and chiral compounds or very complex and specialized functional groups such as the crown compound of cryptand. This invention has unique properties for highly specialized applications such as new pendant functionalized polymers can be produced.

However, in the bonding of Y and/or two groups containing other functional groups, Y and/or Z During the nuclear substitution reactions in which the groups are attached, greater care is taken to ensure that the new functional groups are protected. to ensure that it is not consumed by sequential reactions that produce unplanned crosslinking or gelation. It should also be noted that it is necessary to In some cases, the requested nuclear substitution reaction is completed. It is desirable to protect functional groups that must be preserved until such time as possible.

Most of these types of nuclear substitution reactions can be achieved with the pendant functionalized soluble copolymers of the present invention. The production of these products suffers from some degree of extremely harmful side reactions. It is a high-molecular polymer In some cases, even a small amount of side reaction may cause undesirable gelation and reduce the usefulness of the product. The unique pace polymer of the present invention significantly reduces the claimed nuclear substitution reaction. One of the advantages of using this method is that undesired side reactions can be almost eliminated. Nuclear substitution reactions proceed by several different mechanisms and are common in most electrophiles. In these cases, these different mechanisms may lead to different products or different amounts of side reactions. Are known.

Reactions that proceed with a harmonized SN2-type mechanism are more efficient than reactions that proceed with an Sml-type mechanism. Generally, higher yields of the desired product are obtained. Conjugated benzyl of the invention The advantage of using a halogen as an electrophilic site for nuclear substitution is that the elimination reaction As a result, even reactions proceeding by an Sxl-type mechanism are free from unwanted side effects. The objective is to selectively provide the desired product without reaction.

Another advantage of using the preferred benzylic bromine of the present invention as the site of nuclear substitution is that the substitution reaction Because the reaction proceeds under mild conditions (as benzylbromine is very unstable) , decomposition of the polymer backbone, or thermal recombination or decomposition of reactants or products can be avoided. Is Rukoto. Attached electrophilic site for claimed nuclear substitution as in the present invention By using benzyl halogen and especially benzyl bromine as Other side reactions or sequential reactions, such as those that proceed in Bright soluble pendant-functionalized copolymers are synthesized by selective Sn2-type nuclear substitution reactions. The reactants and conditions can also be selected to allow for the production of the same product. Radiation reaction of the present invention To prepare a backbone saturated soluble polymer with pendant functionalization, It is necessary to carefully adhere to the six "most important" requirements mentioned above.

Various pendant, radiation-reactive, functionalized, soluble, according to the invention The exact and specific conditions suitable for producing saturated copolymers depend on the new official being introduced. depends on the functional group, as well as the composition of the base copolymer and other factors, and each Although experimentation may be necessary to determine the actual conditions for each case, this book does not The most important points mentioned above must always be considered and observed. This means that the following specific Although it will become clearer in the examples, some of the general reaction conditions are determined at the outset. The claimed nuclear substitution reaction can be performed when both the base polymer and the nuclear reactant are soluble. In a solution using a certain solvent system, the base polymer dissolves in one phase and a nuclear reaction occurs. In a two-phase liquid system where a body dissolves in another phase, a two-phase solid/liquid system (i.e. systems in which the base polymer is dispersed in a liquid phase containing the nuclear reactants), or It can be carried out in a cohesive state where the reactants are dissolved or dispersed in the base polymer. can. The common solution is very easy to control and is the preferred case. but, Coagulation reactions can be economically advantageous when suitable reactants and reaction conditions are found. Ru.

Intermediate two-phase systems are advantageous under certain circumstances, and the base polymer (parent) The solubility parameters of nuclear reactants (including electronic materials) and nuclear reactants are so different that a common solvent is Required if not present. In the case of these two phases, the nucleus at the interface between the phases to promote substitution reactions or to transport nuclear reactants to electrophilic sites within the base polymer Therefore, it is often or usually desirable to use a phase transfer catalyst.

A highly preferred method of making pendant functionalized polymers of the invention is benzyl In order to introduce the halogen electrophile, the above-mentioned isobutylene/para-methyls A random copolymer of tyrene is radically halogenated and then base in the same medium without separate recovery of the halogenated polymer. This is a method of introducing a desired new functional group by performing a nuclear substitution reaction depending on the reaction. .

Although it varies depending on the reactivity of the nuclear reactants used and the reaction conditions, the claimed nuclear substitution reaction is carried out at approximately 0°C. temperatures ranging from about 200°C to about 200°C, depending on the claimed nuclear reactants, base polymer and and the thermal stability of the resulting functionalized polymer! 11 limited.

Typically, temperatures of about 0°C to about 150°C are preferred. Reaction times are usually (but so Completion of the claimed nuclear substitution reaction (i.e. electrophile or nuclear reaction) that may not be possible The period of time ranges from a few seconds to 2-3 days. Usually 2 Reaction times of ˜3 minutes to several hours are preferred. The reaction temperature and other conditions are controlled as convenient. The reaction time is set to allow for a long reaction time.

A wide range of solvents/or solvent mixtures can be used as the medium for the claimed nuclear substitution reaction; This element determines whether the reaction is a solution, dispersion, or aggregation reaction. solvent Many factors are important in choosing. be inert under the reaction conditions; be easily removed from the product and easily recycled for reuse in the process. low toxicity under conditions of use and minimal environmental health hazards. It needs to be economical to use, etc. Furthermore, the solvent must provide a favorable reaction environment for the reaction to be carried out. That is, the solvent is The reactants must be in solution contact as intimately as necessary and the desired reaction Intermediate states along the path should make the solvation stable. make the most of the compromises required To achieve this effectively, a single solvent is required: a good solubility of the base polymer that is easy to handle; the other solvent is a good solvent for the nuclear reactants and/or for the intermediates of the reaction. It is necessary or desirable to use solvent mixtures that stabilize the solvation. There are many cases where Random inbutylene/para-methylstyrene copolymer Radical halogenation reaction to introduce electrophile of benzyl halogen, if A suitable solvent for both nuclear substitution reactions and for introducing new pendant functional groups. system, resulting in the need for separate recovery of the halogenated base polymer. It is highly preferred to allow sequential reactions.

Particularly suitable solvents for this sequential reaction route will depend in part on the composition of the base polymer. However, in the case of rubber-elastic base polymers containing a large amount of isobutylene, low boiling point saturated carbonization Hydrogen (C4-Cy) or halogenated hydrocarbon (C+-C7). (Tsu In order to dissolve and bring in the desired nuclear reactant during the desired nuclear substitution reaction, and to carry out the nuclear placement reaction. In order to stabilize the solvation for the conversion reaction, low-boiling alcohols (ci-C4 ) is often desirable. benzene, Aromatic solvents such as toluene and chlorobenzene are commonly It is a good solvent for a whole range of compositions and is a favorable reaction medium for many nuclear substitution reactions. , which often leads to other problems (i.e. benzene during radical halogenation) Due to the toxicity of toluene or the high reactivity of toluene, this first step of the sequential reaction pathway is (This makes them unsuitable as reaction media for The preferred solvent composition is changes when the composition of the mer changes, and the reaction is carried out in solution or in a dispersion. It depends on how big it is. Generally speaking, it contains more para-methylstyrene. , for the tougher, higher Tg base polymers of the present invention, some degree of aroma Solvents with higher solubility parameters containing polyhydric or halogens are required for solution reactions. be done.

Similar precautions are required when considering nucleophilic substitution reactions separately. This reaction For working in liquid, a good solution for the base polymer (depending on its composition) A solvent is required and a co-solvent for the claimed nuclear reactant is also desirable or necessary. It is. A good solvent for the base polymer is listed as suitable for sequential reactions. Although it is similar to the solvent used for radical halogenation, it is better because inertness during radical halogenation is not required. A wide range of solvents may be considered. Low boiling point saturated hydrocarbons (C4-C7) or ha Preference is given to logenated hydrocarbons (CI-C7) and aromatic hydrocarbons or naphthenes.

If you want to make the solvent more polar, you can use tetrahydrofuran or dimethyl Good solvating agents such as diformamide or dimethyl sulfide may also be used. stomach. The latter solvent is also a good solvent for many nuclear reactants and can dissolve the claimed nuclear reactant. used with alcohols or ketones to dissolve and add to the base polymer solution. good.

A solution of the nucleophilic reactant (in a solvent that is miscible with that used for the base polymer) is rapidly This method of adding to the base polymer solution with stirring often A fine dispersion is produced, so that the nucleophilic reactant is dissolved in the mixed solvent formed after addition. Even if complete dissolution is not achieved, substantial solution nuclear displacement reactions may still occur. Na Therefore, the nucleophilic reactant is added during the reaction to replenish the solution concentration as the reaction progresses. This is because it dissolves in

In a more extreme case, i.e. when the claimed nuclear reactant is miscible with the solvent of the base polymer If the co-solvent does not dissolve or the mixed solvent (which keeps the base polymer in solution) If the solubility of the nuclear reactants in the The sppolymer is dissolved in one phase and the claimed nuclear reactant is present in another phase. This way In such cases, good agitation is essential to provide sufficient interfacial contact between the reactants. , and transport the nuclear reactant to the benzylhalogen electrophile site on the base polymer. Phase transfer catalysts are generally desirable. Examples are potassium cyanide, highly polar water-soluble nucleophilic reactants such as sodium sulfate or nitrilotriacetic acid. Ru. Examples of phase transfer catalysts useful in these two-phase reactions include (but are not limited to) (but not limited to): Tetrabutylammonium bromide, Tetrabutylammonium umbisulfate, tetrabutylammonium hydroxide, benzyltrier tylammonium chloride, tetrabutylphosphonium bromide, crown a Tel, Sibutand (c7pluds), Adieu 464, etc. degree. These same types of substances, by providing a specific solvation of the reaction site, It may be beneficial to increase the rate in -phase solution reactions.

The most favorable reaction conditions are to carry out an aggregation reaction, when the nucleophilic reactants are Dissolve or disperse in the base polymer. Working at high solids content requires solvent eliminates the costs of handling and recycling. However, the flocculation reaction requires the use of expensive and inefficient reactors. The extruder has a very high viscosity Although mixing is possible in the system, it limits the reaction medium and therefore only limited nuclear substitution. Only reactions are possible, and even these reactions are limited during the reaction. Side reactions are more likely to occur because conditions and insufficient mixing conditions are more likely to occur.

In the preparation of the pendant functionalized polymers of the present invention, the general reaction described above In addition to specific considerations, factors known (to those skilled in the art) to influence the claimed nuclear substitution reaction include: It applies without materially affecting the invention. In this way, the reaction route and activity The sexualization energy can be controlled by specific solvation or catalysts and can be Reactions can be prevented by shielding, etc.

Example These examples illustrate the specific preparation of several derivatives of benzyl bromide copolymers and their lithography (Iilh-ogr! pbr), corrosion protection, and other Describe its use in coating applications.

Gel refers to the insoluble residue of the rubber in the adhesive, soluble in refluxing toluene for approximately 72 hours. Thoroughly extract the reactive polymer with a solvent, then dry the remaining residue and weigh. It is measured by

The coating is made by dissolving the polymer or formulation in toluene and using Mylar (MYL). AR) or by knife coating on release paper. after that , the coating was dried and irradiated. The coating thickness is typically 1. sumi Le (3,81/1000c+a) There was. UVI shooting is American ultimate Laviolette Minnie Conveyorized Curing Equipment (AierictlσII tsr+olel Mfn+-ConyBorired Coring 57s It was done on Jeil. UV irradiation dose is UVA curing radiation produced by EIT Measured using a meter. EB crosslinking is carried out by Energy Science CB-150. Electro curtain/electron beam accelerator DnerB 5science CB-1 50EIectroci+f1ii! lactamBeII Accelera tor).

Sample of isobutylene/para-methylstyrene/para-bromomethylstyrene The base terpolymer was prepared as follows.

A 500-if reaction flask equipped with a thermometer, stirrer, and addition funnel was heated to installed in a glove box under a moisture-free nitrogen atmosphere to provide a controlled Incubate the flask by immersing it in a heat transfer chamber cooled with liquid nitrogen at a temperature of 19 Cooled to 8°C. To this reactor was added 381i, 6 g of purified dry methyl chloride (purity :99.8%), 47.4g of purified dry distilled polymerized isobutylene (purity: 99%) ．． 9%), and 2.6 g purified dry vacuum distilled para-methylstyrene (all monomers 2.5 mol%) was added. 0.19% by weight of ethyl aluminum in methyl chloride 17 ml of a catalyst solution consisting of chloride (EADC) was then added with stirring. 12 hours while maintaining the temperature by immersing the reactor in a heat transfer bath. Slowly drip into the feed blend from the addition funnel over a period of minutes. Let's cool down However, due to the exothermic polymerization reaction, the reactor temperature remained at 198°C. The temperature rose to -80°C, forming a slurry of polymer in a slightly tan liquid.

Some of the polymer aggregated on the stirrer and reactor walls. 251 cold methanol of the white polymer in a clear colorless liquid by quenching the reactor by adding A cohesive mass was obtained. Evaporate the methyl chloride and knead the polymer in methanol. The polymer was recovered by washing. 0.2% by weight of butylated hydroxy Citoluene (BHT) was added as an antioxidant and the polymer was heated in a vacuum oven at 80°C. Dry in oven. The dry white opaque, tough and rubbery polymer of SOg Recovered. Conversion was 100% with quantitative recovery of polymer. The catalyst efficiency is There was approximately 1550 g of polymer per gram of EADC. The recovered polymer is , has a viscosity average molecular weight (Mv) of 458,000, and has a viscosity average molecular weight (Mv) of 5.2% by weight (2, 5 mol %) of para-methylstyrene. Ultraviolet (UV) and refractive index ( R1) Gel permeation chromatography (GPC) using a detector ) analysis shows that para-methylstyrene is uniformly distributed over the entire molecular weight range. This indicates that a compositionally homogeneous copolymer was formed. ing.

GPC uses Water's Lamgo Max (Isle's Lxm) on the line. bdt-Msx) 481 Waters 150- with LC type UV spectrophotometer CALC/GPC [Millipote Co+ porNioi) was used.

Computer, a division of Beckisi Inc. - Inquiry Systems (ComputerlBair75Ysle) Data collection and analysis were performed using custom software developed by (formerly). Te Various flow rates using trahydrofuran as the mobile phase (but generally 1.Oa+I/ minutes) was used. The apparatus was operated at 30°C at a wavelength of approximately 254 ni for UV. . The polyisobutyne backbone exhibits less absorption compared to aromatic rings at this wavelength. have The column used was α Stiragel (SIHBel) Waters (Wr tus) or Sksdex (Showa Denko). wide pores A set of columns with a narrow molecular weight range from 103 to 4XIO' Calibration was performed using a polystyrene reference sample of fabric. General purpose calibration ( Using wniygtstl ctlib + sth on), polyisobutylene main Molecular weights were reported for the chains. Quantitative output from UV and differential refractometer detectors By comparison, the deviation of the composition from the average can be calculated. In general, the viscosity average molecule Amounts are based on separation measurements in diisobutene at 20°C.

High molecular weight lander of paramethylstyrene and isobutyne prepared as described above. The homogeneous copolymer was placed in a 2 liter resin flask equipped with a stirring blade and jacket. was dissolved in dry n-hexane, but this flask had a four-necked flask top. It was assembled for bromination. Thorough mixing using air-driven turbine mixer , and measured and controlled the temperature using a thermometer and thermocouple, but as explained later, Temperature is controlled by circulating a controlled temperature heat transfer fluid through the jacket. I adjusted it. One of the necks of the flask is used to attach the dropping funnel containing the bromine solution. The bromine solution was added dropwise to the reactor. Wrap the funnel and reactor in foil and let the light shine. I tried not to enter.

Nitrogen injector with sintered glass frit at the end bblCr) on neck 1 and immerse the frit in the solution in the reactor to flush out nitrogen. The rate was set and regulated using a rotometer. the fourth neck A protruding trap (k m e c k -0: i ! + It F r +-” Connect to a-7, 77, several inches during the reaction. Maintain a positive pressure of water to absorb and neutralize all HBr and bromine vapors generated during the reaction. did.

The bromine solution is prepared by drying a weighed amount of bromine over pure molecular sieves in a dropping funnel. n-hexane (essentially olefin-free) and mixed for 30 minutes. Prepared by forming a solution of less than %. wrapped in foil (to prevent light) The bromine addition funnel was attached to a stirred, temperature-controlled, nitrogen-purged reactor. A 500 watt tungsten light was installed immediately adjacent to the reactor.

The reactor was heated to 40°C and the bromine solution was added dropwise. The amount of bromine input is It was 5% by weight. The reaction occurred rapidly when bromine was added, but this was due to the rapid H This was indicated by the evolution of Br and the rapid disappearance of the color of the solution. Bromine for 2 minutes 10 minutes after starting the addition of bromine, react with excess caustic alkali. stopped. The quenched solution was washed with water and washed with alcohol as described above. The brominated copolymer was recovered by precipitation and vacuum oven drying. Before drying, B HT and tetramethylthiuram disulfide as stabilizers at a concentration of 0.1% by weight. mixed into the copolymer. The recovered brominated copolymer is soluble in diisobutylene. Yes, it has an MV of 254.000, and Dietert analysis (D It had 1.26% by weight of bromine as determined by utly+is). 4001H! The presence of 0.9 mol% benzyl bromide groups by analysis using NMR of was shown, and no other brominated structures could be detected.

GPC analysis using UV and RI detectors shows that the brominated copolymer is uniform and homogeneous. Functional copolymer with narrow molecular weight distribution (Mw/Mn=about 2) with composition distribution Pendant functionalized isobutylene containing a quaternary ammonium base being a remer/ Preparation of paramethylstyrene copolymer Example 2A In this example, random isobutylene/para-methylstyrene/para-bromo Tough ionic cross-linked quaternary ammonium salt derivative of momethylstyrene-based terpolymer A conductor was prepared. A base terpolymer was prepared according to the method of Example 1. 2. Contains 4 mol% rose-methylstyrene and has a Mooney viscosity of 30 (ML(H8)1 A random isobutylene/rose-methylstyrene copolymer with Polymerization was carried out in a commercially available 1800 gallon (6813,7 liter) butyl polymerization reactor; After that, I (la gallon (37154 liters) glass-lined Fordler (Pfs) adler) B r reactor with V A Z O52M initiator in hexane solution. Radical bromination was carried out using A base terpolymer having the following was obtained. The composition of this base terpolymer is mol% rose-bromomethylstyrene (0.1 mol% dibrominated rose-bromomethylstyrene) styrene), 11.9 mole % non-brominated rose-methylstyrene, and 97. 7 mol% isobutylene (61% rose-methylstyrene [me r) Due to the relatively high bromination level of J units, a small amount of dibromination and a small fraction molecular weight loss was present). In this nuclear substitution reaction, 450 g of base terpolymer 13 by dissolving it in 2800 g of toluene in a 5 liter resin flask A polymer solution of g51i mass % was prepared, but this flask was It is located under the reflux condenser and goes to the scrubber and blower (tal+bler). It was connected. Then, 47.2 g dissolved in 700 g of isopropanol of triethylamine was slowly added with stirring, and 8G/20 of toluene/ Solution of 11.4% by weight base terpolymer in isopropanol solvent blend was obtained, with a molar ratio of 3 moles of triethanolamine per mole of benzylbromine. Met.

The solution is then stirred under a slight nitrogen purge to a reflux temperature of about 85-86°C. Heated. The solution was stirred and refluxed for 6 hours, then cooled under nitrogen atmosphere. sump Attempts were made on aliquots of water or water/alcohol (70/30) mixture. When shaken with water, the solution emulsified and therefore could not be washed. emal John's pH was 8. When acidified, further adjust the pH to 10 with NaOH solution. Even when raised to ~11, the emulsion remains stable and the solution is still It wasn't separated enough.

Therefore, this functionalized polymer can be recycled by precipitation and kneading in isopropanol. isopropanol and redissolved in a toluene/isopropanol blend. It was further separated from unreacted triethylamine by precipitation in a medium. 0 ．． After mixing 2% by weight of BHT as an antioxidant, the purified functionalized polymer was ．． It was dried in a vacuum oven at 5°C. The recovered and dried polymer is sponge-like and has a slight It was an extremely tough ionic crosslinked elastomer with a yellowish color. benzyl odor A pendant cationic quaternary compound attached to the base terpolymer by elementary nuclear substitution. The ammonium base self-associated to produce a tough ionically crosslinked elastomer. this is Although insoluble in hydrocarbons or alcohols, ion crosslinking occurs through solvation. Easily soluble in a 90/lo toluene/isopropanol mixed solvent that cuts bridges. The interpreted nuclear substitution reaction is shown below.

The analysis summarized below shows that essentially complete substitution of the benzyl bromine has occurred and the pendant It was shown that a quaternary ammonium salt functionalized polymer was produced.

Mv 270.000 27G, 000Br weight% 2.6 2.2 N weight% 0.34 M.R. Benzyl Br mol% 1.4- 4th mol% 1.4 Paramethylstyrene mol% 0.9 0.9 Proton NMR spectrometer (spccl rogrsph) is co-coupled with benzylic hydrogen adjacent to bromine at 447 ppm. The resonance disappeared and two new resonances appeared, one of which was due to the bend adjacent to the quaternary nitrogen. one at 4,1 ppm due to dihydrogen, and the other at 4,1 ppm due to nitrogen It was at 3.5 ppm with tyrene hydrogen. rose-methylstyrene The resonance at 2 to 3 ppm due to the disparate methyl hydrogen connected to the ``unit'' is due to a nuclear substitution reaction. There was no change.

Proton NMR resonance of the bound “mer” unit CHz-C)lx A portion of the dried pendant functionalized polymer of this example was dissolved in 90/10 toluene. A 15% by weight solution was obtained by dissolving in a mixed solvent of chlorine/isopropanol. This solution It was cast onto a glass plate and the solvent was evaporated to form a tough rubbery film. . Excellent adhesion to glass after drying in a vacuum oven at 70°C An extremely tough ionically crosslinked film was deposited in this way. This fi The lume could be redissolved with a mixed hydrocarbon/alcohol solvent blend. Similarly, Impregnation of the solution into the support by immersion followed by evaporation of the solvent blend Therefore, tough ionically crosslinked elastomers can be used in a variety of porous substrates (i.e., coarse woven fabrics). ) to produce a waterproof fabric coated with a tough ionic crosslinked elastomer. Ta. This waterproof fabric withstood water droplets, shed water, and was water resistant when used. child The elastomer has the high bactericidal properties characteristic of quaternary ammonium salts. was also expected. This quaternary ammonium salt functionalized polymer has high strength, toughness, and Many water-based It may also be useful in adhesive and bonding applications. It is water resistant, environmentally resistant Gold resistance, good adhesion, and corrosion protection properties of cationic ionomers are desirable. It would also work well as a corrosion-inhibiting coating on metal. (extractability, poison without the need for the addition of vulcanizing agents (with associated problems of performance, cost, and other Ability to self-crosslink through ionic self-association without heat vulcanization is a highly desirable property of this cationically functionalized polymer.

Example 2B In this example, a pendant functionalization containing a cationic quaternary ammonium base is used. A stable emulsifier-free emulsifier-free emulsifier-free emulsifier-free emulsifier-based copolymer was prepared based primarily on isobutylene. Transformed into Tex. with a Mv of 45.000 and 2 mol% of para-chloromethane An isobutylene-based polymer containing Rustyrene “mer” units was prepared at 70/30 Torr. 2 gallons (7,57082 liters) A 35% by weight solution was formed by shaking overnight in a 100ml container. This melt The solution was diluted with 1.4 times the stoichiometric amount of triethylamine (based on the amount of benzyl chlorine). I put it in a 5 liter "ELF J" resin flask along with the bottle, but this The flask was assembled as described in Example 2. Do not stir the solution. The mixture was then heated to 82° C. for 4 hours to complete the nuclear substitution reaction. Pendant functionalization for analysis A summary of copolymer sample recovery is described in Example 2. The collection process is , precipitation and kneading in isopropanol, reconstitution in toluene/isopropanol including dissolution and redeposition in isopropanol and subsequent use as an antioxidant. It is mixed with 0.2% by weight of BHT and dried in a vacuum oven at 70°C. purified and dried The pendant-functionalized copolymer is an extremely tough white flake that reacts well with toluene. is insoluble, but in a 90/1G toluene/isopropanol solvent blend. It was ionically crosslinked as indicated by easy dissolution. Analysis Ben It was shown that complete conversion of dichlorine to quaternary ammonium base had occurred. times The copolymer obtained contained 0.48% nitrogen by weight, and NMR analysis showed that 2 mol. % of benzyltriethylammonium chloride base.

The remainder of the cooled reaction effluent solution is combined with distilled water in a 40/60 water/solution volume ratio. A stable oil-in-water emulsicon was obtained by simply mixing to obtain a stable oil-in-water emulsicon. This emulsion First, use a dispersion machine (dispe+sst++rL) and then use a colloid mill. After purification, a very stable fine-grained latex was obtained. This raw latex is Remove some of the solvent and water by stripping by heating with stirring. A stable finished latex containing 50% solids was obtained. To manufacture this latex No emulsifier was required. Manufacturing and stripping are added as emulsifiers. Typical experience in manufacturing, stripping, and concentrating latex, including soaps easily achieved without any problems.

Castings from this finished latex were dried and used in the solution mold of run fl12A. Transparent, hydrophobic, strong ionic cross-linking as described for cast films A film was formed. This cationic latex, which does not contain emulsifiers, has this strong Dip products, binders, nonwovens, and coatings of ionically crosslinked, cationically functionalized polymers. In the host of applications including adhesives, radiation crosslinkable pressure sensitive adhesives, etc. enable use. This tough, ionically cross-linked, cationically functionalized polymer has excellent It may be advantageous due to aging and environmental resistance, as well as other unique properties.

Example 3 Pendant functionalized isobutylene/substituted para-methyl containing quaternary phosphonium bases Preparation of styrene copolymers In this example, the cationic quaternary phosphonium base Preparation of pendant functionalized primarily isobutylene-based copolymers containing It was converted into a stable latex containing no emulsifier. It has a Mv of 17.000 , isobutylene containing 1.9 mol% rose-chloromethylstyrene "mer" units The base polymer is a 75/25 hebutane/isopropyl alcohol solvent blend. 40% by weight of the pot in a 5 liter "L" resin flask. A reamer solution was formed. This reactor is equipped with dry water-cooled low temperature fingers (dB +Cε- C65! ε、ICG! a, 1B=t) so that the C condensate is refluxed into the flask. several inches of the scrubber and reactor for exhaust gases through the was connected to a squirt to maintain a positive pressure of water. slow dry nitrogen was maintained through the system to keep the reactants under a dry, inert atmosphere. at 25℃ Chemical (based on benzylchlorine) while stirring and maintaining a dry nitrogen atmosphere Twice the stoichiometric amount of triethylphosphine in a 67% wt solution in isopropanol It was added dropwise from a sealed dropping funnel. Heat the mixture to 77°C with stirring. It was heated to reflux temperature and refluxed for 2 hours with stirring under nitrogen, then cooled. pen A sample of Danto-functionalized polymer was collected from the resulting clear effluent solution for analysis. . The dust recovery process involves precipitation and kneading in isopropanol, hexane/isopropanol This includes re-dissolution into Patur solvent and redecipitation from isopropanol. After that, G as an antioxidant was mixed with 2% by weight of BHT and placed in a vacuum oven at 70°C. dry. Despite its very low molecular weight, the recovered polymer has strong elastic properties. a flexible, sticky, semi-liquid starting base terpolymer was very different. Analysis shows that this polymer contains 0.95 mol% phosphorus. This indicates that the transition from benzyl chlorine to the quaternary phosphonium base is approximately This indicates that 50% conversion has occurred.

The remainder of the cooled solution from the nucleophilic substitution reaction is mixed with distilled water and a 40/60 water/solution solution. A stable oil-in-water emulsion was obtained by simply mixing at the same volume ratio. this Emulsicone was purified and then stripped and concentrated as in Example 2B. A stable, emulsifier-free, fine-grained cation containing 50% solids by weight. obtained latex. The production and stripping of this latex was similar to Example 2B. Capping is easily accomplished without any problems, and capping from this latex is When dried, sting is useful in a wide range of applications, such as those already outlined. A hydrophobic, transparent, and tough ionically crosslinked elastic film was formed.

The pendant functionalized polymer in this latex is designed to prevent the nuclear substitution reaction from proceeding completely. Because of the high It was. However, the presence of 1 mol% of quaternary phosphonium chloride base does not result in stable milk production. It is suitable for allowing the production of latex without additives and is suitable for the production of adhesive polymer films. It was suitable for forming ionic crosslinks in the film. The presence of benzyl chlorine is , allow permanent covalent crosslinks to be formed in a number of ways, or This would allow for other reactions to be performed on the dandy-functionalized polymer.

This nuclear substitution reaction is shown below.

CH2CH2 The analysis shows that this reaction occurs without degradation or cross-linking and under the conditions of this experiment. , 50% conversion of benzylic chloride to quaternary phosphonium chloride salt groups was achieved. It was shown that by longer reaction times and/or higher reaction temperatures; or Higher conversions could be achieved by selecting a more favorable reaction medium. Dew.

Examples 2 and 3 all contain various pendant cationic functional groups. It has been demonstrated that chain saturated pendant functionalized copolymers can be easily prepared according to the method of the present invention. and that they have a combination of properties that are useful in a variety of applications. It shows. The pendant cationic groups provide self-emulsifying properties and are free from emulsifiers. It enables the easy production of cationic latex and also allows for the production of pendant The thionic groups self-associate in the dry deposited film and undergo reversible ionic reaction by appropriate solvation. resulting in on-crosslinking.

Although two types of cationic pendant functionalized copolymers have been illustrated (i.e. Ammonium salts and quaternary phosphonium salts), others such as sulfonium salts It is also possible, for example, using thioethers as shown below as nuclear reagents. be.

1←CHz-C)I H--←CHx-CHH-Cth CHI2 BI　S"lh　Br- The properties of these cationic pendant functionalized copolymers are that the attached cations Vary and control depending on the type of group as well as the R group and counter ion present. A wide range of properties is possible. Therefore, the inventors found that triethyl Although only quaternary ammonium salts and phosphonium salts are illustrated, other R groups may also be used. Quaternary salts with 100% are also easily prepared and provide improved properties. Generally, the R group is small As the size decreases (i.e. from ethyl to methyl), the ionic association becomes stronger and difficult to cleave. However, as the R group becomes larger, the hydrophobicity improves. The characteristic is counterion (i.e., chlorine, bromine, bisulfate, etc.). similar In addition, the properties of the S-isothiouronium salt as a claimed nuclear reagent (used in the examples of this application) whether thiourea itself was used (as in A lot depends on how strong it is.

Both ionic crosslink strength and hydrogen bonding properties were used to prepare the salts. As the R groups of substituted thioureas become larger and longer, they become smaller. Ma In addition, the R group itself contains other functional groups and cations containing other useful functional groups. salts can be prepared. For example, as a claimed nuclear reagent, triethanolamine pendants containing quaternary ammonium salts with hydroxyl functionality using Functionalized polymers can be prepared to enable other reactions or for adhesion or dispersion effects. promote, etc.

→CH2-Ca1-÷--CH2-CH-÷-:N [CH2CH20H] 3+ l 1C) I2CH! Or　N”　[C1hCH20[1]　a　Br-Furthermore, in this specification, examples are However, by attaching a pendant anionic group, carboxylate or It is also possible to prepare anionic pendant functionalized polymers such as sulfonates. It is obvious to those skilled in the art that this is possible.

Preparation of functionalized isobutylene/paramethylstyrene copolymer Example 4A In this example, sodium diethyldithiocarbamate is used as the charging nuclear reagent. Randomize the pendant dithiocarbamate ester functionality by nuclear substitution using Muisobutylene/para-methylstyrene/para-bromomethylstyrene base star - attached to a polymer. Base star polymer containing reactive electronic benzylic bromine was prepared as previously described. The starting polymer was prepared as in Example 1. Manufactured. It contains 3.3 mol% para-methylstyrene and has a viscosity of 68,000 It had a high average molecular weight. The polymer was prepared in hexane using a photoinitiator at 40 °C. Radically brominated as a 15% solution of , a base terpolymer containing 4.3% by weight of bromine was obtained. This base star polymer The composition is 96.7 mol% isobutylene, 2.6 mol% para-bromomethyl Rustyrene, and 0.7 mole % para-methylstyrene. Highly brominated water Some dibrominated para-methylstyrene was present because the standard was achieved. child In the nuclear substitution reaction, 200 g of the base terpolymer was reacted with 5 liters of 8.7% by weight dissolved in 2100 g of toluene in a toluene resin flask. A polymer solution was prepared.

Then add 22 g of diethyldithio dissolved in 700 g of isopropyl alcohol. Slowly add the sodium carbamate at room temperature with stirring and add 75/25 A 6.6 wt% solution of the polymer in a toluene/isopropanol solvent blend The obtained nuclear reagent had a ratio of 1.2 moles per mole of Br. stir the solution heating at 80°C for 6 hours under a nitrogen atmosphere to complete the nuclear substitution reaction, and then , cooled. However, the samples taken after 1 hour and 3 hours had 80 After 1 hour at 0.degree. C., the reaction was already shown to be complete. Wash the cooled solution several times with water. The sodium bromide by-product and other water solubles were removed and then the example described above Similarly, the polymer was recovered by precipitation and kneading in isopropanol.

The attached dithiocarbamate ester group itself acts as a polymer bond stabilizer. The polymer was dried in a vacuum oven at 70°C without the addition of stabilizers. It was dry. The recovered polymer is a tough, slightly yellow elastomer. , completely dissolved in hexane. The analysis summarized below shows that benzyl bromine to dithi It was shown that a very high conversion to ocarbamate ester was achieved.

-ToCH2-CH publication- B" words hc-S-C-N [Etl 2 M　v　65.00G　65.000 Br weight% 4.3 o, a Sulfur weight% 2,97 N weight% 0.65 M.R. Benzyl Br mol% 2.6- Dithiocarbamate 2.6 Ester mole% The proton NMR spectrum shows the pendant dithiocarba from the benzyl bromine functional group. Chemical analysis was confirmed showing quantitative conversion to mate ester functionality.

Prototype of attached pendant functional dithiocarbamate ester “mer” unit NMR resonance proton resonance (ppm) This experiment claims that the benzyl bromine functionality in the base terpolymer via nuclear substitution can be easily converted into pendant dithiocarnocomate ester functional groups. It was shown that The attached pendant dithiocarbamate ester functionality is Antioxidant protection against polymers including vulcanization and co-vulcanization (cotalc 1 txtion) activity and enables use in the radical reaction described below.

Example 4B In this example, isobutylene/vala-methylstyrene/vala-bromomethyl Styrene-based terpolymers were prepared and intermediate-based Pendant dithiocarbamates without separate isolation and recovery of the terpolymer was converted into a copolymer containing ester functional groups. Intermediate-based terpolymer times This sequential reaction route, which does not require a reaction, is naturally economically advantageous.

An isocontaining material containing 2.4 mol% rose-methylstyrene and having a Mooney viscosity of 3G. Butylene/rose-methylstyrene random copolymer (as used in Example 2A) copolymer) in hexane under a nitrogen atmosphere to give a 17% by weight solution. Atomite (ATOMI) formed and stirred in suspension as an acid scavenger TEI ClCo 18% by weight was added to obtain an opaque white slightly viscous solution. . This was heated to 60° C. with stirring under a nitrogen atmosphere. Apply this solution to 120 watts. Continue stirring at 60°C under a slight nitrogen purge while illuminating with a spotlight. 6.5% by weight of bromine based on the polymer as a 20% by weight solution in hexane. and added. As bromine was added, the solution turned bright orange/red; This color quickly disappeared when the radical bromination reaction took place. Even if the solution is opaque However, the photoinitiated bromination proceeded rapidly, so that the bromine color completely disappeared within 5 minutes. I turned off the light. Brominated Paster - Take a sample of the polyination solution and then , 1 mole of sodium diethyldithiocarbamate per mole of bromine is Added as a 5% solution by weight in Patur, H/20 hexane/isopropyl This solution was stirred at a high temperature of 60°C to carry out the nuclear displacement reaction. I set it. Samples taken at 15 minute intervals as the reaction progresses within 0.5 hours. indicated that the reaction was complete. Dilute the sample and final solution with HCI (1%) Wash several times with water to convert excess ClCO3 to CxC1z, and add it and other water-soluble The solids were removed into an aqueous wash solution. Wash this solution several more times with water to remove trace amounts of acid. followed by precipitation and kneading in isopropanol as in the example above. The polymer was recovered by

In the first step of this sequential reaction, the starting copolymer has a The styrene moiety is converted to a bara-bromomethylstyrene moiety by photoinitiated radical bromination. The by-product HBr is removed by reaction with dispersed calcium carbonate. It will be done.

Brz → 2 B".

start CHa・CFh ・Ch　C[12Br Radical chain bromination process 2HB++ClCO3-+C5Brz10zCh acid scavenging method In the second step of the sequential reaction, sodium diethyldithiocarbamate nucleophile The drug reacts with electronic benzylic bromine to generate the desired pendant functionalized product .

[H] 2N-C-5-”Nx + CH2r -’i-C1h-CH publication- HzC-5-C-N[Efl12 amount The analysis summarized below shows that the intermediate based terpolymer has a benzyl odor of 1.2 mol%. containing elementary functional groups, while the final pendant functionalized product contains 0.9 mol% dithioca rubamate ester pendant functional group and 0.3 mol% benzyl bromine functional group residue. It was shown that it contains

Mw 28,000 28.0G0 2g, 0110B "Weight% 2.0G, 5 8% by weight 1.O N weight% 0.2 NMR PMS mol% 2.3 1.1 1. IBrPMS mol% 1.2 0.3 dithiocarba Mate mol% 0.9 This mixed functional polymer is stable without the addition of antioxidants and is capable of accelerated oxidation. It could be vulcanized using zinc and/or conventional sulfur vulcanization systems. This polymer is It also showed good co-vulcanization in blends with natural rubber. This copolymer fill The film crosslinked without degradation when exposed to UV irradiation, but this was due to the high isobutylene content. This was in contrast to the degradation that occurred when the polymers were exposed to UV radiation.

Crosslinking under irradiation is stable when the dithiocarbamate ester functional group is exposed to irradiation. can easily form radicals and are usually bundled in isobutylene-based polymers. Enables radical cross-linking and other radical chemical reactions rather than backbone cleavage This is due to this.

l light H2C-3-C-N[H]2 ■ 1←CH2−CH−’J− 1hC1・5-CN[El]2 Prevent cross-linking UV deterioration due to coupling insertion reaction, etc. and/or This dithiocarbamate ester functionality provides controlled cross-linking under conditions. Ability to apply outdoors such as roofing, painting, white tire sidewalls, etc. of great value in applications. In such applications, deterioration and surface viscosity Isobutylene-based copolymers with increased adhesion may have their usefulness compromised. Put it away.

In Example 4 In the example, approximately equal amounts of dithiocarbamate ester functionality and benzyl bromine Pendant functionalized isobutylene-based copolymers containing functional groups are It was prepared by a sequential reaction route without recovery of the terpolymer.

An isocontaining material containing 4.5 mol% para-methylstyrene and having a Mooney viscosity of 34. 500g of butylene/para-methylstyrene random copolymer under nitrogen atmosphere Dissolved in 2833 g of n-hexane in a 5 liter resin flask to yield 15 % solution was obtained. As an acid scavenger, 45 g OMYACORB ) UFT calcium carbonate was stirred to obtain an opaque white suspension. Then this The solution was heated to 60°C with stirring and illuminated with a 120 watt spotlight. . 35 g of bromine (7% by weight based on polymer) in a 25% by weight solution in hexane A base terpolymer was produced by adding the base terpolymer as a radical bromination agent. bromine The reaction was completed within 5 minutes. Characterization of brominated-based terpolymers After removing the sample for sorption, it was dissolved in 600 g of isopropanol. (gives an 83/17 hexane/isopropanol solvent blend) Sodium ethyldithiocarbamate (0.9 mol per mol of bromine) was added. A claimed nuclear substitution reaction was carried out. This solution was stirred at a high temperature of 60°C for 0.5 hours to react. completed. After the solution was cooled and washed with acid, it was washed with alcohol as in Example 4B. The polymer was recovered by precipitation. The sequential reactions proceeded as previously described.

The analysis summarized below shows that the intermediate base terpolymer contains 2.2 mol% bromine. , while the final pendant mixed functionalization product contains 0.7 mol % benzyl bromine functionality. and 0.7 mol% of dithiocarnocmate ester functional groups. did.

Moony 34 33.5 33 Br weight% 2.2 1. O5 S weight% 0.77 N weight% 0,17 NMR FMS mol% 4.5 3.1 3.18rPMS mol% 1.4 0.7 dithiocarbamate Ester mol% -0,7 These examples show that pendant dithiocarbamate ester functional groups are It was shown that it can be easily introduced into the base terpolymer of the present invention. benzyl odor A stable compound containing both elementary functional groups and dithiocarbamate ester pendant functional groups. Mixed functional polymers can be prepared with desired functional group ratios, allowing for economical sequential reaction routes. Available.

Example 5 Pendant functionalized isobutylene/paramethylstyrene containing various ester functional groups Preparation of Copolymer Example 5A In this example, by nuclear substitution using cinnamate as the charging nuclear reagent, the Random mate ester functional group isobutylene/para-methylstyrene/para- attached to a bromomethylstyrene-based terpolymer.

The base terpolymers used in this example were those of Examples 4A and 4B. 0.9 mol% brominated para-methylstyrene, Contains 1.4 mol% para-methylstyrene and 97.7 mol% isobutylene. It had a Mv of 135.000.

In a nucleophilic substitution reaction, 750 g of the base terpolymer was stirred under a nitrogen atmosphere. 3000 in a 5 liter resin flask with an air condenser connected. A 20% by weight polymer solution was prepared by dissolving in 10 g of toluene. Next, 35 ．． 4 g of cinnamic acid (1.5 moles per mole of bromine), 40 wt. 77.3 g of trabutylammonium hydroxide solution (0.5 g per mole of acid) mol), and 9.6 g of a 50% by weight aqueous sodium hydroxide solution (0 per mol of acid) , 5 mol) with stirring, and the resulting emulsion was heated to 86°C with continued stirring. The mixture was heated to reflux temperature. The solution was refluxed at 86°C for 3 hours to complete the reaction. but at the beginning of reflux, 0.5 h after reflux, and 1.5 h to monitor the progress of the reaction. Samples were removed after an hour. During the reaction, the solution gradually became clear. 3 o'clock After a while, the solution was clear and light beige in color. Acid wash and salt on final solution and sample Base cleaning and neutral cleaning were performed. Then, similar to the above example, isopropyl 0.2% by weight of BHT was recovered by precipitation in a mold and kneaded as an antioxidant. The mixture was mixed and dried in a vacuum oven at 70°C. Princeton - Gamma Chick ( Analysis was performed using a Primeceton-Gtmig Tecb) bromine analyzer. Ta. The following is a summary of the bromine remaining in the starting polymer with respect to the degree of reaction: However, this is because the nuclear substitution reaction progressed slowly and was not completed even after 3 hours of reflux. It shows.

Progress of reaction Bromine weight% Starting base terpolymer l, 60 At the start of reflux 1.37 0.5 hours later 1.08 1.5 hours later 0.91 3 hours later (final) 0.54 After 3 hours of reflux, the final product contains 0.8 mol% cinnamate ester and 0.1 mol % benzylbromine, the claimed nuclear substitution reaction was about 90% complete.

r Hi Proton NMR fraction was used to quantify the amount of cinnamate ester functionality introduced. Optical analysis was used.

Of course, new aromatic protons were also present in the spectrograph.

This experiment attempts to synthesize pendant carboxylic acid esters by nuclear substitution reaction under appropriate conditions. It has been shown that functional groups can be introduced into the base terpolymer of the present invention. Shinname The toester functional group emits actinic radiation when the polymer is irradiated. Crosslinking can be caused by eye diction.

Example 5B In this example, the fatty acid is lylunic acid (Liteco Corporation (Wi INDUS Corporation manufactured by tco Corporation. penda by nuclear substitution using commercially available C18 fatty acids in Random isobutylene/para-methylstyrene/para-methylstyrene was attached to a bromomethylstyrene-based terpolymer. used base The terpolymer has a Mooney viscosity of 30 and contains 2 mol% para-bromomethyl. Rustyrene, 5 mol% para-methylstyrene, and 93 mol% isobutylene It contained.

In a nucleophilic substitution reaction, 500 g of the base terpolymer was added to air under a nitrogen atmosphere. 21133 g Torr in a 5 liter resin flask connected to a condenser A 15% by weight polymer solution was prepared by dissolving in Ene. Next, 63.3g of Industrin 12G flaxseed fatty acids (1.2 moles per mole of bromine) 72.8 g of a 40% by weight solution of tetrabutylammonium hydroxide in alcohol (0.5 mol per mol of acid), and 9 g of 50% by weight aqueous sodium hydroxide solution (0.5 mol per mol of acid). The emulsion formed is opaque It used to be bright and slightly yellow.

Next, this was heated to a reflux temperature of 87° C. under a nitrogen atmosphere while stirring. this The emulsion was refluxed for 2 hours, but at the beginning of reflux to monitor the progress of the reaction. Samples were taken after 0.5 and 1 hour of reflux. During the reaction the solution gradually It became clear and the water was distilled and went into the condenser. The final solution is clear and bright It was a bright yellow color. Acid wash, base wash, and neutralization of reaction samples and final reaction effluent Washing is applied, after which the polymer is precipitated in isopropanol as before, Vacuum oven dried.

The same analysis as in Example 5A regarding bromine remaining in the starting polymer is summarized below. However, this is because the nuclear substitution reaction with Cl11 fatty acid is faster than the reaction with cinnamate, and it takes about 1 hour. showed that it was essentially completed in between. The claimed nuclear reagent bound to the C17 hydrocarbon is the base terpolymer than the carboxylate group attached to the shorter aryl group. The necessary close contact with the benzylbromine electrophile bound to was more easily achieved. That is clear.

Progress of reaction Bromine weight% Starting base terpolymer 3.0 At the start of reflux 1.06 0.5 hours later 0.45 1.5 hours later 0.29 3 hours later (final) 0.23 MMR analysis shows that the re-terminated product contains 2 mol% ester and essentially no benzyl bromine. This shows that the nuclear substitution reaction has been completed.

(The small residual bromine content measured by the bromine analyzer probably occurred during the recovery process. It represents inorganic bromine that has not been completely washed away. ) NMR spectrum (hereinafter (shown below) is co-coupled with benzyl ester protons at 5.08 ppm1. due to the olefinic proton in the Cl11 chain at 5.3-5.5 ppm. It shows a wide and complex resonance.

By comparison, the benzyl ester proton of the cinnamate ester of Example 5A is Due to the conjugation present in the cinnamate ester, it is more concentrated at 5.2 ppm. It showed high field resonance.

The fully converted linseed oleate derivative of this example remains fully soluble. Zinc oxide or accelerated zinc oxide (these are (effective for brominated “base” terpolymers) showed no evidence of vulcanization crosslinking, indicating the absence of residual benzyl bromine. This is one piece of evidence. However, this functionalized polymer It exhibited good vulcanization when cured in combination with sulfur systems.

Polymer 100 Sulfur 1.25 M, Tag (Ding odds) 1.50 Altax (^1tIt1 1.00 Zinc oxide 3.00 Therefore, the presence of unsaturation in the pendant fatty acid side chain contributes to the functional Conventional sulfur vulcanization systems can be used to vulcanize the activated ester derivatives. . Pendant unsaturation can also be used with highly unsaturated general purpose rubbers such as natural rubber or SBR. enables co-vulcanization of The sulfur content of this ester derivative in the standard ozone resistance test When yellow-vulcanized samples were tested, it was found that the saturated base terpolymer vulcanizate showed significant It was shown that it possesses excellent ozone resistance characteristics. Pendant unsaturation in the side chain is Thus, conventional sulfur vulcanization activity can be used without adversely affecting ozone resistance. In the example, the fatty acid bases a pendant fatty acid ester functional group containing conjugated unsaturation. - attached to star polymer. The fatty acids used were derived from tung oil. and was rich in nireostearic acid. The base terpolymer is 32 mooni -viscosity, 3.6% by weight of bromine, 2.2% by mole of para-bromomethyl Styrene, 2.7 mol% para-methylstyrene, and 95.1 mol% isobutylene. In the claimed nuclear substitution reaction that involved tyrene, 666 g of "wet" base tarpo Add small pieces of reamer (500 g dry weight) to the 5 liters connected to the air condenser. Contains water dissolved and dispersed in 2833 g of toluene in a plastic flask Using the "wet" pieces in a nuclear substitution reaction in which a 15% by weight polymer solution was prepared. The use of This is advantageous because it eliminates the need for finishing before converting.

To this polymer solution was added 76 g of tung oil acid (approximately 1.2 moles per mole of bromine), 87.4 of a 40% by weight solution of tetrabutylammonium hydroxide in tanol g (0.5 mol per mol of acid), and 43 g of 50% by weight aqueous sodium hydroxide. The solution (0.2 mol per mol of acid) was added to give a milky white emulsion.

This was heated to reflux temperature of about 84°C. The reaction mixture was kept under constant stirring for 1 hour. Refluxed, then cooled, washed and collected as described above. Similarly, the opening of reflux Samples were taken at the beginning and after 0.5 hours of reflux.

The substitution reaction proceeds rapidly under these conditions, as shown by the bromine analysis below. I went.

Progress of reaction Bromine weight% Starting base terpolymer 3.6 At the start of reflux 0.78 0.5 hours later 0.56 3 hours later (final) 0.4O The NMR spectrum (shown below) shows the benzyl ester at 5.08 Nm Resonance due to protons, how much at 4,47 ppm 1 due to residual benzyl bromine 5, 3 to 6.4 p due to the residual resonance and the olefinic proton of the C10 acid. A series of resonances at pa+l (conjugated unsaturated resonances are >s, high frequency at 9 ppm) This is the resonance of the field. The final product contains 1.9 mol% ester and 0.2 mol% of residual benzyl bromine. This is completely possible in toluene. It was soluble and had the same Mooney viscosity of 31 as the starting base terpolymer.

Despite the high activity of the pendant conjugated unsaturation, this functionalized polymer does not dry or had good stability with no tendency to crosslink during storage. however, Combined conjugated unsaturation can be easily vulcanized using sulfur vulcanization systems or combined with unsaturated rubbers. Vulcanization could be performed. This conjugated unsaturation results in good crosslinking under electron beam irradiation. It also resulted in oxidative surface hardening when exposed to sunlight outdoors. This is roof painting This is a highly desirable property for outdoor applications such as painting. This conjugate unsaturation is It is also very active in chemical reactions, and therefore, it is highly active in reactions with radically polymerizable monomers. Enable raft reactions. This highly active kyryoyl acid ester derivative has a wide range of Useful in applications.

Nuclear substitution reactions with various carboxylic acids have been performed using ricinoleic acid, etc. It is clear that it can be used to attach many other functional side chains such as Pace isobutylene/para-methylstyrene prepared in the same manner as in Example 1. Starting from an intermediate/para-bromomethylstyrene terpolymer intermediate, UV light initiation The agent benzophenone is converted into a 4-benzoylbenzoate ester derivative as described above. – Incorporated into polymers.

Mechanical stirrer, hose connector, nitrogen purged, operated under nitrogen atmosphere 801 was added to a 2501 glass reaction vessel equipped with a septum (1ξ pjum). 10 g of base terpolymer (Mooney viscosity -32 , 1,88% by weight of bromine). In the second flask under a nitrogen atmosphere. , 0.51 g of 4-benzoylbenzoic acid and tetrabutylammonium hydroxy (2.2 ml, LM in methanol) was dissolved in 251 toluene, then this Tetrabutylammonium and 4- A toluene solution of benzoyl benzoate was prepared. Next, another 0.09g of 4-benzoylbenzoic acid was dissolved in 251 of toluene, and this was added to the second solution. The solution was added dropwise until it became weakly basic. This solution was added to the first solution. of this mixture The temperature was raised to 70°C and the reaction was continued for 6 hours. After finishing, dissolve the polymer in methanol. It was deposited from a vacuum oven at 1 mmH! s Dry at 40°C. 4-Ben Analysis (NMR, IR) for zoylbenzoate content was Complete conversion of rustyrene to 4-benzoylbenzoate ester was shown.

This functionalized polymer has a Mooney viscosity of 32 and 0.75 mol% 4-benzene. Contains zoyl benzoate ester. Film (1,5 mil) on release paper and exposed to UV radiation. As can be seen from Table 1, this functionalized polymer showed good crosslinking response at low absorption levels.

Examples 8-11 In the following examples, 3-benzoyl benzoate (Example 8), 2-benzoyl benzoate (Example 8), Zoylbenzoate (Example 9), 4-hydroxybenzophenone (Example 10) ), and derivative functionalization of anthraquinone-2-carboxylate (Example II) A copolymer was prepared by nuclear substitution reaction according to Example 7 and the photoinitiator benzo Incorporated phenone, hydroxybenzophenone, or anthraquinone. implementation Pace isobutylene/para-methylstyrene/para prepared as in Example 1 - Bromomethylstyrene terpolymers are identical and have a Mooney viscosity of 32. It had 1.88% bromine by weight. UV-functionalized copolymer 0.75 mol% It contained esters. In each reaction, 2.0 g of base terpolymer It was used. The initial amount of 3-benzoylbenzoic acid was 0.11 g, An additional 0.02 g was added to neutralize. The amount of 2-benzoylbenzoic acid used is 3 - Same as for benzoylbenzoic acid. anthraquinone-2-carboxylic acid The amount was 0.12g, and the amount of 4-hydroxybenzophenone was 0.09g. Ta.

For gelation studies, films (1.5 mil) were formed on release paper. Table 1 The data show that the photoinitiated graft polymers of these examples also have significant effects at low UV absorption levels. It was shown that it had a strong crosslinking response.

Table I 7 4-benzoylbenzoate 94 95 958 3-benzoylbenzo ate 90 89 1199 2-benzoylbenzony) 68 112 7911 1-nthraquinone-2-carbo beef shill) 83 85 8g1 Torr Percentage of insoluble material after ene extraction Examples 12-19 For the cinnamate-functionalized copolymer prepared similarly to Example 5A, the variable to determine the level of gel formation in the amount of coating thickness and amount of UV exposure. The test was conducted. The base terpolymer has a Mv of approximately 135.000 and 0 ．． 2.3 mol% para-methylstyrene containing 9 mol% brominated para-methylstyrene It was composed of tyrene. This is accomplished via bromination and sequential nucleophilic substitution reactions. was converted to the polymer of Example 5A, which contained 0.1 mol% para-bromomethyl It contained styrene and 0.8 mole percent cinnamate ester. This thin name The functionalized copolymers were crosslinked via UV-initiated 2+2 photocycloaddition. results It is shown in Table ■.

From that data, thin coatings with high UV exposure and low wt% functional groups It can be seen that the highest degree of cross-linking occurred in the sample.

■Table +2 0.8 0.3 0.09 44+3 0.8 0.3 0.17 51 14 0.8 0.3 0.25 34IS O,80,30,4219 +6 0.8 0.6 0.14 6917 0.8 0.6 0.17 73 180.8 0.6 0.37 64 +9 0.8 0.6 0.57 36 Examples 20-21 In the following examples, the 4-hydroxybenzophenone functionality from Example 1O copolymers as anti-corrosion coatings on galvanized steel plates. used.

First, the polymer of Example 1G was dissolved in toluene, then two sheets of zinc plating It was applied on a scratched steel plate.

Evaporation of the solvent resulted in a 1 mil thick film coating. 1 piece One plate was cross-linked by 0.24 J# UV irradiation, but the other plate was not cross-linked. There wasn't.

The corrosion resistance of the plates was observed after immersion in a 5% NaCl salt bath for 10 days. both The plate protected the galvanized steel plate from corrosion, but it was not cross-linked. Boards with a film protect against corrosion penetration under the outer edge of the protective film coating. It was showing. The advantages of crosslinking film coatings are corrosion and non-polar solvents. improved resistance to Potential applications for such materials include the automotive industry. This prevents corrosion.

Example 22 In the following example, the 4-hydroxybenzophenone functionalized copolymer from Example 10 The polymer was used as a coating in lithographic applications. Example A 1 mil thick film was deposited onto a cardboard support as described in 20-21. Coated. UV light of 0.25 Vd is passed through the photographic negative onto the dry film. and irradiated to form a stencil-type image in the coating. present in toluene The image was developed by imaging and removing uncrosslinked polymer.

The detailed description of the invention is illustrative and various modifications thereof will occur to those skilled in the art. Any such invention that comes within the scope and spirit of the appended claims may readily occur to you. Modifications are intended to be encompassed by this invention.

Claims (1)

[Claims] 1. A lithographic coating comprising an isoolefin of 4 to 7 carbon atoms. Radiation-crosslinked functionalized polymers of phosphorus and para-alkyl styrene comonomers lithography comprising a functionalized polymer having a substantially uniform compositional distribution, - image of the comonomer attached to the para-alkyl group of the para-alkylstyrene. wherein said polymer is functionalized with a radiation-reactive group in said functionalized polymer. A coating containing an image that has been cross-linked by radiation. 2. Claim 1 wherein the functionalized polymer has a number average molecular weight of at least about 5000. coating. 3. the functionalized polymer has a number average molecular weight of about 5000 to 500,000; The coating of claim 1. 4. The functionalized polymer has a weight average molecular weight to number average molecular weight ratio of about 6 or less. The coating of claim 1 comprising: 5. At least about 95% by weight of the functionalized polymer satisfies the average parameter of the functionalized polymer. - para-alkylstyrene content within about 10% by weight of the alkylstyrene content; 2. The coating of claim 1, comprising: 6. Isoolefins include isobutylene and para-alkylstyrenes include para-alkylstyrenes. 2. The coating of claim 1, comprising tylstyrene. 7. 7. The code of claim 6, wherein the functionalized polymer has a number average molecular weight of about 5000 or more. Ting. 8. The functionalized polymer has a weight average molecular weight to number average molecular weight ratio of about 6 or less. 8. The coating of claim 7, comprising: 9. Isoolefins and para-alkylstyrenes are present in functionalized polymers. The fins constitute about 10 to 99.5% by weight of the polymer and include para-alkyl styrene. the polymer is present in an amount such that it constitutes about 0.5 to 90% by weight of the polymer; The coating of claim 1. 10. The isoolefin contains isobutylene, and the para-alkylstyrene contains para-alkylstyrene. 10. The coating of claim 9, comprising methylstyrene. 11. Functionalized polymers make para-alkylstyrene ▲Mathematical formulas, chemical formulas, tables, etc. Masu▼ where R and R' are independently hydrogen, alkyl, halogenated selected from the group consisting of primary and secondary alkyl groups, and Y is a hydrogen- and radiation-reactive functional group. 2. The coating of claim 1, comprising a mixture of. 12. R and R' are independently hydrogen, C1-C5 alkyl, halogenated C1- The coating of claim 11 selected from the group consisting of C5 primary and secondary alkyl groups. Ng. 13. The radiation-reactive functional group is benzophenone, 4-chlorobenzophenone, 4 -Hydroxybenzophenone, benzoquinone, naphthaquinone, anthraquinone, 2-chloroanthraquinone, benzylidene acetophenone, acetophenone, protein Ropiophenone, cyclopropylphenyl ketone, benzaldehyde, β-naph Tylphenyl ketone, β-naphthaldehyde, β-acetonaphthone, 2,3-pene ntandione, benzil, fluorenone, benzanthrone, Michler's ketone, bis(parahydroxybenzylidene)acetone, benzoin, selected from the group consisting of deoxybenzoin and chlorodeoxybenzoin 12. The coating of claim 11, comprising a nucleophilically substituted photoinitiator. 14. Claims wherein the radiation-reactive functional group comprises a nucleophilically substituted thioxanthone Item 11 Coating. 15. The radiation-reactive functional group is N,N-disubstituted dithiocarbamic acids and their a nucleophilically substituted photoinitiator selected from the group consisting of esters and salts; The coating of claim 11. 16. the radiation-reactive functional group is from the group consisting of tung oil acid and its esters and salts; 12. The coating of claim 11, comprising a selected nucleophilically substituted photoinitiator. 17. The radiation-reactive functional group is benzoic acid, cinnamic acid, m-nitrocinnamic acid, p-chloro cinnamic acid, p-methoxycinnamic acid, chalcone acrylic acid, p-phenylene bis(alpha) Acrylic acid) p-azidobenzoic acid, p-sulfonazidebenzoic acid, α-cyanocinnamic acid Acid, cinnamylidene acetic acid, cinnamylidene malonic acid, α-cyanocinnamylidene Acetic acid, β-(1)-naphthyl acrylic acid, β-(2)-furfuryl acrylic acid, α-cyano-β-(2)-thienyl acrylic acid, β-(1)-naphthyl acrylic acid acid, consisting of β-(9)-anthryl acrylic acid, and their esters and salts. 12. The coating of claim 11, comprising a photoinitiator selected from the group. 18. further comprising about 5 to about 95 parts by weight of a tackifier blended with the polymer. The method of claim 1, wherein the sum of parts by weight of the polymer and the tackifier is 100. coating. 19. 19. The coating of claim 18, wherein the tackifier comprises about 30 to about 70 parts by weight. Ng. 20. Para-alkyl styrene is present in the functionalized polymer. I'm here▼ where R and R' are independently hydrogen, alkyl, halogenated selected from primary and secondary alkyl groups, and W is selected from hydrogen, X, Y, and Z. , where X is chlorine or bromine, Y is a radiation-reactive functional group, and Z is oxygen, sulfur. , silicon, nitrogen, carbon, or sodium, potassium, lithium, and magnesium a non-radiation-reactive functional group containing a metal selected from para- The alkylstyrene comprises from about 0.5 to about 99.5% by weight of the polymer; The para-alkylstyrene in which is Y represents about 0.5% to about 55% by weight of the polymer. and W is X, the para-alkylstyrene constitutes % and W is Z of the polymer. up to 55% by weight, and the functionalized polymer has a number average molecular weight of about 5000 or more. The coating of claim 1 comprising: 21. The para-alkylstyrene in which W is hydrogen is about 1 to 10% of the functionalized polymer. The para-alkyl styrene, comprising about 2% by weight and where W is Y, accounts for about 2% by weight of the polymer. The para-alkylstyrene constituting 0.5 to about 55% by weight and in which W is para-alkyl styrene comprising up to about 20% by weight of the polymer and where W is Z Wren constitutes 0 to about 55% by weight of the polymer, and the polymer contains about 5000% A number average molecular weight of from about 500,000 to a weight average molecular weight of about 6 or less. 21. The coating of claim 20, having a ratio to amount. 22. The para-alkylstyrene in which W is hydrogen is about 2 to 30% of the functionalized polymer. The para-alkylstyrene comprising about 10% by weight and where W is Y is of the polymer. The para-alkylstyrene comprising about 0.5 to about 55% by weight and where W is para-alkyls comprising up to about 15% by weight of the polymer and wherein W is Z The tyrene comprises 0 to about 55% by weight of the polymer, and the polymer has about 500% by weight. Number average molecular weight of 0 to about 500,000 and a weight average molecular weight of about 6 or less 21. The coating of claim 20, having a molecular weight to molecular weight ratio. 23. The para-alkylstyrene in which W is hydrogen is about 1 to 10% of the functionalized polymer. The para-alkyl styrene comprising about 7% by weight and W is Y represents about 7% by weight of the polymer. para-alkylstyrene comprising 0.5 to about 55% by weight and W is X comprises about 1% by weight or less of the polymer, and the polymer comprises about 5,000 to about 5% by weight of the polymer. For a number average molecular weight of 00,000 and a weight average molecular weight of about 6 or less 21. The coating of claim 20, having a ratio of: 24. The functionalized polymer is essentially free of para-alkylstyrene, where W is 21. The coating of claim 20. 25. The para-alkylstyrene in which W is X constitutes less than about 1% by weight of the polymer. 21. The coating of claim 20, comprising: 26. A method of forming a lithographic image on a surface, the method comprising: (1) Isoolefins of 4 to 7 carbon atoms and para-alkylstyrene comonomers a radiation-crosslinkable functionalized polymer having a substantially uniform composition distribution; The comonomer is a radiation-crosslinkable group in the para-alkyl group of the para-alkylstyrene. coating at least a portion of the surface of the article with a functionalized polymer that is functionalized with a step of (b) exposing said surface to a specific pattern of radiation to form a lithographic image; crosslinking the remer. 27. prior to the exposing step, further comprising forming an image of the pattern on the surface. 3. The imaging step comprises selectively preventing transmission of electromagnetic radiation. Method 6. 28. 28. The method of claim 27, wherein a portion of the polymer is not crosslinked after the exposing step. 29. Remove the non-crosslinked polymer and develop the crosslinked polymer pattern. 29. The method of claim 28, further comprising the step of: 30. 30. The method of claim 29, wherein the removing step includes washing the surface with a solvent. . 31. etching the pattern through the cross-linked coating on the surface; 30. The method of claim 29, further comprising transferring to the surface. 32. further comprising removing the cross-linked coating from the etched surface. 32. The method of claim 31. 33. Claim wherein said removing step comprises chemical or plasma treatment of said coating. The method of Section 32. 34. The coating step applies a solution of a polymer to the surface and removes the solvent. 27. The method of claim 26, comprising: leaving a film of the polymer on a surface. 35. The coating step includes applying a hot melt of a polymer to the surface. 27. The method of claim 26, comprising: 36. Claim 2, wherein the crosslinking radiation comprises ultraviolet radiation, electron beam, or gamma radiation. Method 6. 37. If the item is metal, paper, wood, plastic, cloth, glass, ceramic, or graphite, 27. The method of claim 26, comprising: 38. A corrosion and solvent resistant rubber produced by the method of claim 26. Articles with rear coating. 39. A lithographically imaged surface produced by the method of claim 26. 40. Etching resistant patterned product produced by the method of claim 29. Articles with a painted coating. 41. 30. An article having a printed element produced by the method of claim 29. 42. 32. An etched article produced by the method of claim 31. 43. 33. An etched article produced by the method of claim 32.